CN111856882A - Composition for forming silicon-containing resist underlayer film and pattern forming method - Google Patents

Composition for forming silicon-containing resist underlayer film and pattern forming method Download PDF

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Publication number
CN111856882A
CN111856882A CN202010333047.5A CN202010333047A CN111856882A CN 111856882 A CN111856882 A CN 111856882A CN 202010333047 A CN202010333047 A CN 202010333047A CN 111856882 A CN111856882 A CN 111856882A
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China
Prior art keywords
film
silicon
resist
pattern
resist underlayer
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CN202010333047.5A
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Chinese (zh)
Inventor
荻原勤
渡边司
美谷岛祐介
金山昌广
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Shin Etsu Chemical Co Ltd
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Shin Etsu Chemical Co Ltd
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Publication of CN111856882A publication Critical patent/CN111856882A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
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    • G03F7/075—Silicon-containing compounds
    • G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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    • H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32139—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer using masks

Abstract

The present invention relates to a composition for forming a silicon-containing resist underlayer film and a pattern forming method. The invention provides a resist underlayer film capable of improving LWR and CDU in a fine pattern formed from a chemically amplified resist using an acid as a catalyst. The silicon-containing resist underlayer film forming composition contains a thermosetting silicon-containing material (Sx), a curing catalyst (Xc) and a solvent, and the diffusion distance of the curing catalyst (Xc) from a resist underlayer film formed from the silicon-containing resist underlayer film forming composition to a resist overlayer film formed on the resist underlayer film is 5nm or less.

Description

Composition for forming silicon-containing resist underlayer film and pattern forming method
Technical Field
The present invention relates to a composition for forming a coating type silicon-containing resist underlayer film used for lithography in the manufacturing process of semiconductor devices and the like, and a pattern forming method using the composition.
Background
With the demand for finer pattern rules with higher integration and higher speed of large scale integrated circuits (LSIs), photolithography using chemically amplified resists, which is currently being used as a general-purpose technology, has been developed in various technologies as to how finer and more precise patterning can be performed with respect to the light source used.
On the other hand, as miniaturization progresses, the diffraction phenomenon of light approaches the physical limit, and accordingly, the contrast of exposure light used for pattern formation also decreases more and more. Such physical limitation causes a decrease in the solubility contrast of the positive resist film, which results in deterioration in the resolution and focus latitude of the hole pattern and the trench pattern. As a technique for preventing deterioration of the pattern forming performance in such a limit state, it is necessary to improve the dissolution contrast of the resist film. In the case of chemically amplified resists, attempts have been made to improve the solubility contrast by increasing the sensitivity and minimizing the effect of lowering the contrast of exposure light by utilizing the mechanism of propagation of acid generated from a photoacid generator.
The influence of the acid propagation mechanism causes deterioration of edge roughness (LWR) and size uniformity (CDU) of the hole pattern. The reason is considered to be the influence of concentration and aggregation of the base polymer and the acid generator, but the influence of diffusion of the growing acid cannot be ignored. Further, in order to prevent pattern collapse in the fine pattern, thinning of the resist film has progressed, but LWR and CDU tend to deteriorate as the resist film is thinned. As the resist pattern is miniaturized, the deterioration of LWR and CDU is a serious problem because the increase of acid for improving contrast and the thinning for preventing collapse are mutually affected.
Thus, in the resist pattern formed by the thinning, there is a problem that the dry etching selectivity cannot be secured for the purpose of pattern transfer to the substrate. Therefore, a pattern transfer process using a multilayer resist method using a silicon-containing film as a resist underlayer film is generally employed. In ArF lithography, it is known that a composition for forming a silicon-containing resist underlayer film is used, which contains a curing catalyst (patent document 1). It has been proposed to use a curing catalyst also for a silicon-containing resist underlayer film forming composition in EUV lithography (patent document 2). The hardening catalyst has a structure suitable for forming a siloxane bond through condensation of silanol, but has a structure similar to that of the sensitivity adjuster in the upper resist. Therefore, when the curing catalyst diffuses into the upper resist during or after exposure, the patterning capability at the interface between the resist upper film and the silicon-containing lower film, particularly the LWR and CDU performance, is affected, and it is necessary to improve the resist lower film performance.
[ patent document 1] Japanese patent application laid-open No. 2007-302873
[ patent document 2] International publication No. 2013/161372 booklet
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide a resist underlayer film which can improve LWR and CDU in a fine pattern formed from a chemically amplified resist using an acid as a catalyst.
Means for solving the problems
In order to achieve the above object, the present invention provides a composition for forming a silicon-containing resist underlayer film, comprising a thermosetting silicon-containing material (Sx), a curing catalyst (Xc) and a solvent,
the curing catalyst (Xc) has a diffusion distance of 5nm or less from a resist underlayer film formed from the silicon-containing resist underlayer film forming composition to a resist overlayer film formed on the resist underlayer film.
As will be described later, the curing catalyst (Xc) that diffuses from the silicon-containing resist underlayer film to the resist overlayer film neutralizes the acid in the overlayer resist that is generated by exposure. Therefore, the removal of acid-releasing groups in the resist upper layer film is inhibited, and the resin constituting the resist upper layer film, which is not dissolved in the developer, remains at the interface between the resist upper layer film and the silicon-containing resist lower layer film, causing the deterioration of LWR and CDU of the resist pattern. The silicon-containing resist underlayer film forming composition of the present invention can form a silicon-containing resist underlayer film that can exhibit the original performance of a resist underlayer film without causing such deterioration of LWR and CDU, by setting the diffusion distance of the curing catalyst (Xc) to 5nm or less.
As the aforementioned curing catalyst (Xc), sulfonium salt (Xc-1), iodonium salt (Xc-2), phosphonium salt (Xc-3), ammonium salt (Xc-4), or polysiloxane (Xc-10) having a partial structure thereof, or an alkali metal salt is preferred.
When the curing catalyst (Xc) is the specific one, the silicon-containing resist underlayer film forming composition can form a silicon-containing resist underlayer film that further exhibits the original performance of a resist underlayer film.
The total number of carbon atoms contained in the organic group forming the cationic portion of the curing catalyst (Xc) is preferably 9 or more.
When the cation moiety of the curing catalyst (Xc) is as described above, the silicon-containing resist underlayer film forming composition can form a silicon-containing resist underlayer film that further exhibits the original performance of a resist underlayer film.
Further, the present invention provides a pattern forming method comprising the steps of:
forming an organic film on a workpiece by using a coating type organic film material;
forming a resist underlayer film on the organic film by using the silicon-containing resist underlayer film forming composition;
forming a resist upper layer film on the resist lower layer film by using a resist upper layer film composition composed of a photoresist composition;
Forming a circuit pattern on the resist upper layer film;
transferring a pattern to the resist underlayer film by etching using the resist underlayer film on which the circuit pattern has been formed as a mask;
transferring the pattern to the organic film by etching using the resist underlayer film to which the pattern has been transferred as a mask;
transferring a pattern to the object by etching using the organic film having the transferred pattern as a mask.
Furthermore, the present invention provides a pattern forming method, comprising the steps of:
forming a hard mask containing carbon as a main component on a workpiece by a CVD method;
forming a resist underlayer film on the hard mask by using the silicon-containing resist underlayer film forming composition;
forming a resist upper layer film on the resist lower layer film by using a resist upper layer film composition composed of a photoresist composition;
forming a circuit pattern on the resist upper layer film;
transferring a pattern to the resist underlayer film by etching using the resist underlayer film on which the circuit pattern has been formed as a mask;
transferring the pattern to the hard mask by dry etching using the resist underlayer film to which the pattern has been transferred as a mask;
Transferring the pattern to the workpiece by dry etching using the hard mask to which the pattern has been transferred as a mask.
By the above pattern forming method, the solubility of the resist upper layer film in the vicinity of the interface between the resist upper layer film and the silicon-containing resist lower layer film can be improved, and the residue of the resin constituting the resist upper layer film remaining in the vicinity of the interface can be eliminated, whereby a pattern improved in LWR and CDU of the resist pattern can be formed.
The patterning of the resist upper layer film is preferably performed by photolithography with a wavelength of 10nm to 300nm, direct writing with an electron beam, nanoimprinting, or a combination thereof.
The pattern formation in the resist upper layer film can more fully exhibit the effects of the present invention if specified as described above.
The object to be processed is preferably a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film or a metal oxide nitride film.
When the workpiece is specified above, the effects of the present invention can be more fully exhibited.
The metal constituting the workpiece is preferably silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or an alloy thereof.
The effect of the present invention can be more fully exhibited when the metal constituting the workpiece is the specific metal.
ADVANTAGEOUS EFFECTS OF INVENTION
The silicon-containing resist underlayer film forming composition of the present invention, which contains the curing catalyst (Xc) having a diffusion distance of 5nm or less from the resist underlayer film to the resist overlayer film, can form an overlayer resist pattern having good LWR and CDU properties, and has excellent dry etching selectivity between the resist overlayer film and the organic film or the hard mask, thereby forming a pattern for a semiconductor device on a substrate with good yield. Further, the composition for forming a silicon-containing resist underlayer film of the present invention can obtain high etching selectivity with respect to an organic material, and thus a formed photoresist pattern can be sequentially transferred to a silicon-containing resist underlayer film, an organic film, or a hard mask by using a dry etching process. In particular, in recent semiconductor device manufacturing processes with progress in miniaturization, multiple exposure processes are often used, and LWR and CDU of a pattern after development have a large influence on device performance. Therefore, improvements in LWR, CDU performance are important. The silicon-containing resist underlayer film forming composition of the present invention has a good dry etching selectivity, and even when the silicon-containing resist underlayer film is used as a dry etching mask, deformation of the resist underlayer film pattern during dry etching can be suppressed, and excellent LWR and CDU can be maintained, and transfer to a substrate with high accuracy can be performed.
Drawings
Fig. 1 shows a schematic view of an example of the method for measuring the diffusion distance of the curing catalyst (Xc) according to the present invention.
Detailed Description
As described above, there is a need for development of a resist underlayer film capable of improving LWR and CDU in a fine pattern formed using a chemically amplified resist using an acid as a catalyst.
The present inventors have made an effort to solve the above-mentioned problems, and as a result, have found a curing catalyst (Xc) which can easily measure the diffusion distance of the curing catalyst (Xc) in a silicon-containing resist underlayer film into a resist underlayer film without using an expensive EUV exposure apparatus and which does not affect LWR and CDU in EUV lithography, and have completed a composition for forming a silicon-containing underlayer film using the curing catalyst (Xc).
That is, the present invention is a composition for forming a silicon-containing resist underlayer film, comprising a thermosetting silicon-containing material (Sx), a curing catalyst (Xc) and a solvent,
the curing catalyst (Xc) has a diffusion distance of 5nm or less from a resist underlayer film formed from the silicon-containing resist underlayer film forming composition to a resist overlayer film formed on the resist underlayer film.
The present invention will be described in detail below, but the present invention is not limited thereto.
[ thermosetting silicon-containing Material (Sx) ]
The thermosetting silicon-containing material (Sx) of the present invention may be a thermosetting polysiloxane containing at least one of a repeating unit represented by the following general formula (Sx-1), a repeating unit represented by the following general formula (Sx-2), and a partial structure represented by the following general formula (Sx-3).
[ solution 1]
Figure BDA0002465657770000061
In the formula, R1、R2、R3Each of which is a 1-valent organic group having 1 to 30 carbon atoms, which may be the same or different.
The thermosetting silicon-containing material (Sx) can be produced by hydrolytic condensation of the following hydrolyzable monomer (Sm).
Specific examples of the hydrolyzable monomer (Sm) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltriisopropoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltripropoxysilane, methyltripropoxysilane, and the like, Isopropyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, butyltriisopropoxysilane, sec-butyltrimethoxysilane, sec-butyltriethoxysilane, sec-butyltripropoxysilane, sec-butyltriisopropoxysilane, tert-butyltrimethoxysilane, tert-butyltriethoxysilane, tert-butyltripropoxysilane, tert-butyltriisopropoxysilane, cyclopropyltrimethoxysilane, cyclopropyltriethoxysilane, cyclopropyltripropoxysilane, cyclopropyltriisopropoxysilane, cyclobutyltrimethoxysilane, cyclobutyltriethoxysilane, cyclobutyltripropoxysilane, cyclobutyltriisopropoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyltripropoxysilane, cyclohexyltrimethoxysilane, Cyclohexyltriethoxysilane, cyclohexyltripropoxysilane, cyclohexyltriisopropoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, cyclohexenyltripropoxysilane, cyclohexenyltriisopropoxysilane, cyclohexenylethyltrimethoxysilane, cyclohexenylethyltriethoxysilane, cyclohexenylethyltripropoxysilane, cyclohexenylethyltriisopropoxysilane, cyclooctyltrimethoxysilane, cyclooctyltriethoxysilane, cyclooctyltripropoxysilane, cyclooctyltriisopropoxysilane, cyclopentylpropyltrimethoxysilane, cyclopentylpropyltriethoxysilane, cyclopentylpropyltripropoxysilane, cyclopentylpropyltriisopropoxysilane, bicycloheptenyltrimethoxysilane, bicycloheptenyltriethoxysilane, bicycloheptenyltripropoxysilane, tricycloheptenyltripropoxysilane, cyclohexyltripropoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, cyclohexenyltripropoxysilane, cyclohexenyl, Bicycloheptenyl triisopropoxysilane, bicycloheptyl trimethoxysilane, bicycloheptyl triethoxysilane, bicycloheptyl tripropoxysilane, bicycloheptyl triisopropoxysilane, adamantyl trimethoxysilane, adamantyl triethoxysilane, adamantyl tripropoxysilane, adamantyl triisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, benzyltripropoxysilane, benzyltriisopropoxysilane, anisyl trimethoxysilane, anisyl triethoxysilane, anisyl tripropoxysilane, anisyl triisopropoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, tolyltripropoxysilane, tolyltriisopropoxysilane, and mixtures thereof, Phenethyltrimethoxysilane, phenethyltriethoxysilane, phenethyltripropoxysilane, phenethyltriisopropoxysilane, naphthyltrimethoxysilane, naphthyltriethoxysilane, naphthyltripropoxysilane, naphthyltriisopropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, dimethyldipropoxysilane, dimethyldiisopropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldiisopropoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dipropyldipropoxysilane, dipropyldiisopropoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldipropyldipropoxysilane, diisopropyldiisopropoxysilane, diisopropyltrimethoxysilane, naphthyltriisopropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldiisopropoxysilane, dimethyldiethoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dibutyldipropoxysilane, dibutyldiisopropoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyldipropoxysilane, di-sec-butyldiisopropoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyldipropoxysilane, dicyclopropyldimethoxysilane, dicyclobutyldimethoxysilane, dicyclobropyldipropoxysilane, dicyclopropyldimethoxysilane, dicyclobutyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclopentyldipropoxysilane, dicyclopentyldiisopropoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldimethoxy, Dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclohexyldipropoxysilane, dicyclohexyldiisopropoxysilane, dicyclohexyldimethoxysilane, dicyclohexylhexenyldiethoxysilane, dicyclohexylhexenyldipropoxysilane, dicyclohexylethyldimethoxysilane, dicyclohexylethyldiethoxysilane, dicyclohexylhexenylethyldipropoxysilane, dicyclohexylethyldipropoxysilane, dicyclohexylethyldiisopropyloxysilane, dicyclooctyldimethoxysilane, dicyclooctyldethoxysilane, dicyclooctyldimethoxysilane, dicyclooctyldiisopropoxysilane, dicyclopentadienylpropyldimethoxysilane, dicyclopentadienylpropyldiethoxysilane, dicyclopentadienylpropyldipropoxysilane, dicyclopentadienylpropyldiisopropoxysilane, dicyclopentadienylpropyldimethoxysilane, dicyclopentadienyldimethoxysilane, bis (bicycloheptenyl) dimethoxysilane, bis (bicycloheptenyl) diethoxysilane, bis (bicycloheptenyl) dipropoxysilane, bis (bicycloheptenyl) diisopropoxysilane, bis (bicycloheptyl) dimethoxysilane, bis (bicycloheptyl) diethoxysilane, bis (bicycloheptyl) dipropoxysilane, bis (bicycloheptyl) diisopropoxysilane, diamantalkyldimethoxysilane, diamantalkyldiethoxysilane, diamantalkyldipropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldiisopropoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethylethylmethoxysilane, diphenyldimethoxysilane, bis (bicycloheptyl) diisopropoxysilane, di (bicyclohe, Dimethylethylethoxysilane, dimethylphenylmethoxysilane, dimethylphenylethoxysilane, dimethylbenzylmethoxysilane, dimethylbenzylethoxysilane, dimethylbenzylethyloxysilane, and the like.
As the above-mentioned compounds, preferred are, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexenyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, trimethylmethoxysilane, dimethylethylmethoxysilane, dimethylphenylmethoxysilane, dimethylbenzylmethoxysilane, dimethylphenylethylmethoxysilane and the like.
To the aforementioned R1、R2、R3Other examples of the organic group include organic groups having 1 or more carbon-oxygen single bonds or carbon-oxygen double bonds. Specifically, the organic group includes 1 or more groups selected from the group consisting of ether bond, ester bond, alkoxy group, hydroxyl group, and the like. Examples thereof include those represented by the following general formula (Sm-R).
(P-Q1-(S1)v1-Q2-)u-(T)v2-Q3-(S2)v3-Q4-
···(Sm-R)
In the general formula (Sm-R), P is a hydrogen atom, a cyclic ether group, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an alkylcarbonyloxy group having 1 to 6 carbon atoms or an alkylcarbonyl group having 1 to 6 carbon atoms, Q1、Q2、Q3And Q4Each independently is-CqH(2q-p)PpWherein P is an integer of 0 to 3, q is an integer of 0 to 10 (provided that q 0 represents a single bond), u is an integer of 0 to 3, and S is as defined above1And S2Each independently represents-O-, -CO-, -OCO-, -COO-or-OCOO-. v. of1、v2And v3Each independently represents 0 or 1. Examples of T which is a 2-valent atom other than carbon, a 2-valent group composed of an alicyclic ring, an aromatic ring, or a heterocyclic ring, and T which also contains a heteroatom such as an oxygen atom, are shown below. In T, Q2And Q3The position of the bond is not particularly limited, and may be appropriately selected in consideration of the reactivity of the steric factor, availability of a commercially available reagent used for the reaction, and the like.
[ solution 2]
Figure BDA0002465657770000101
Preferable examples of the organic group having 1 or more carbon-oxygen single bonds or carbon-oxygen double bonds in the general formula (Sm-R) are as follows. In the following formula, (Si) is described for showing a bonding site with Si.
[ solution 3]
Figure BDA0002465657770000111
[ solution 4]
Figure BDA0002465657770000121
[ solution 5]
Figure BDA0002465657770000131
And, with R1、R2、R3As examples of the organic group of (3), organic groups having a silicon-silicon bond may also be used. Specific examples thereof include the following.
[ solution 6]
Figure BDA0002465657770000132
And, with R1、R2、R3As examples of the organic group (2), organic groups having a protecting group which is decomposed by an acid can also be used. Specifically, there may be mentioned organic groups listed in paragraphs (0043) to (0048) of Japanese patent application laid-open No. 2013-167669, and organic groups derived from silicon compounds listed in paragraph (0056) of Japanese patent application laid-open No. 2013-224279.
Further, with respect to R1、R2、R3As examples of the organic group of (2), organic groups having a fluorine atom may also be used. Specifically, there may be mentioned organic groups derived from silicon compounds as shown in paragraphs (0059) to (0065) of Japanese patent laid-open No. 2012-53253. And R is1、R2、R3Examples of the organic group of (2) may also use an organic group having a nitrogen atom or a sulfur atom.
The hydrolyzable monomer (Sm) has 1, 2 or 3 hydrolyzable groups bonded to the silicon atom represented by the partial structure (Si), such as chlorine, bromine, iodine, acetoxy, methoxy, ethoxy, propoxy or butoxy groups.
[ Synthesis method of thermosetting silicon-containing Material (Sx) 1: acid catalyst
The thermosetting silicon-containing material (Sx) of the present invention can be produced by subjecting a mixture of 1 or 2 or more types of hydrolyzable monomers (Sm) to hydrolytic condensation in the presence of an acid catalyst.
Examples of the acid catalyst used in this case include organic acids such as formic acid, acetic acid, oxalic acid and maleic acid, hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid and toluenesulfonic acid. The amount of the catalyst used is preferably 1 mole per 1 mole of the hydrolyzable monomer (Sm)10-6About 10 mol, preferably about 1X 10-5About 5 mol, more preferably about 1X 10-4About 1 mole.
When the thermosetting silicon-containing material (Sx) is obtained by hydrolysis condensation of the monomer, the amount of water is preferably 0.01 to 100 mol, more preferably 0.05 to 50 mol, and still more preferably 0.1 to 30 mol per 1 mol of the hydrolyzable substituent bonded to the hydrolyzable monomer (Sm). When the amount of water is 100 mol or less, the apparatus used for the reaction is small, and the method is economical.
In terms of the operation method, the hydrolyzable monomer (Sm) is added to the aqueous catalyst solution to initiate the hydrolytic condensation reaction. In this case, the organic solvent may be added to the aqueous catalyst solution, the hydrolyzable monomer (Sm) may be diluted with the organic solvent in advance, or both may be carried out. The reaction temperature is preferably 0 to 100 ℃, more preferably 5 to 80 ℃. The monomer is preferably added dropwise while maintaining the temperature at 5 to 80 ℃ and then aging at 20 to 80 ℃.
As the organic solvent which can be added to the aqueous catalyst solution or can dilute the hydrolyzable monomer (Sm), methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, acetone, acetonitrile, tetrahydrofuran, toluene, hexane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl pentanone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, methyl ethyl acetate, methyl acetate, ethyl acetate, methyl acetate, Gamma-butyrolactone, and the like, and mixtures of the foregoing, and the like are preferred.
Among the above solvents, those which are water-soluble are preferable. For example: alcohols such as methanol, ethanol, 1-propanol and 2-propanol, polyhydric alcohols such as ethylene glycol and propylene glycol, polyhydric alcohol condensate derivatives such as butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether and ethylene glycol monopropyl ether, acetone, acetonitrile and tetrahydrofuran. Among them, those having a boiling point of 100 ℃ or lower are particularly preferable.
The amount of the organic solvent to be used is preferably 0 to 1,000ml, more preferably 0 to 500ml, based on 1 mole of the hydrolyzable monomer (Sm). When the amount of the organic solvent used is not more than the upper limit, the reaction vessel is small, and the cost is economical.
Then, if necessary, a neutralization reaction of the catalyst is carried out to obtain an aqueous reaction mixture solution. The amount of the basic substance to be used for neutralization is preferably 0.1 to 2 equivalents based on the acid used for the catalyst. The alkaline substance may be any substance as long as it is alkaline in water.
Then, it is preferable to remove by-products such as alcohols generated by the hydrolytic condensation reaction from the reaction mixture by, for example, reducing the pressure. In this case, the temperature for heating the reaction mixture depends on the kind of the organic solvent added and the alcohol generated in the reaction, and is preferably 0 to 100 ℃, more preferably 10 to 90 ℃, and still more preferably 15 to 80 ℃. The degree of pressure reduction at this time varies depending on the kind of organic solvent, alcohol, etc. to be removed, the exhaust device, the condensing device, and the heating temperature, and is preferably not more than atmospheric pressure, more preferably not more than 80kPa, and still more preferably not more than 50 kPa. The amount of alcohol to be removed at this time is difficult to be precisely known, and it is preferable to remove about 80 mass% or more of the alcohol or the like produced.
The acid catalyst used in the hydrolytic condensation may then be removed from the reaction mixture. The acid catalyst is removed by mixing water with the solution of the thermosetting silicon-containing material (Sx) and extracting the thermosetting silicon-containing material (Sx) with an organic solvent. The organic solvent used in this case is preferably one which dissolves the thermosetting silicon-containing material (Sx) and separates into 2 layers when mixed with water. Examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl pentanone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ -butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether and the like, And mixtures of the foregoing.
Further, a mixture of a water-soluble organic solvent and a sparingly water-soluble organic solvent may be used. For example: methanol-ethyl acetate mixture, ethanol-ethyl acetate mixture, 1-propanol-ethyl acetate mixture, 2-propanol-ethyl acetate mixture, butanediol monomethyl ether-ethyl acetate mixture, propylene glycol monomethyl ether-ethyl acetate mixture, ethylene glycol monomethyl ether-ethyl acetate mixture, butanediol monoethyl ether-ethyl acetate mixture, propylene glycol monoethyl ether-ethyl acetate mixture, ethylene glycol monoethyl ether-ethyl acetate mixture, butanediol monopropyl ether-ethyl acetate mixture, propylene glycol monopropyl ether-ethyl acetate mixture, ethylene glycol monopropyl ether-ethyl acetate mixture, methanol-methyl isobutyl ketone mixture, ethanol-methyl isobutyl ketone mixture, 1-propanol-methyl isobutyl ketone mixture, methanol-ethyl acetate mixture, ethylene glycol monomethyl ether-ethyl acetate mixture, ethylene glycol monoethyl ether-ethyl acetate mixture, ethylene glycol monopropyl ether-ethyl acetate mixture, 2-propanol-methyl isobutyl ketone mixture, propylene glycol monomethyl ether-methyl isobutyl ketone mixture, ethylene glycol monomethyl ether-methyl isobutyl ketone mixture, propylene glycol monoethyl ether-methyl isobutyl ketone mixture, ethylene glycol monoethyl ether-methyl isobutyl ketone mixture, propylene glycol monopropyl ether-methyl isobutyl ketone mixture, ethylene glycol monopropyl ether-methyl isobutyl ketone mixture, methanol-cyclopentyl methyl ether mixture, ethanol-cyclopentyl methyl ether mixture, 1-propanol-cyclopentyl methyl ether mixture, 2-propanol-cyclopentyl methyl ether mixture, propylene glycol monomethyl ether-cyclopentyl methyl ether mixture, ethylene glycol monomethyl ether-cyclopentyl methyl ether mixture, propylene glycol monoethyl ether-cyclopentyl methyl ether mixture, ethylene glycol monoethyl ether-cyclopentyl methyl ether mixture, propylene glycol monoethyl ether-methyl ether mixture, propylene glycol monoethyl ether, Propylene glycol monopropyl ether-cyclopentyl methyl ether mixture, ethylene glycol monopropyl ether-cyclopentyl methyl ether mixture, methanol-propylene glycol methyl ether acetate mixture, ethanol-propylene glycol methyl ether acetate mixture, 1-propanol-propylene glycol methyl ether acetate mixture, 2-propanol-propylene glycol methyl ether acetate mixture, propylene glycol monomethyl ether-propylene glycol methyl ether acetate mixture, ethylene glycol monomethyl ether-propylene glycol methyl ether acetate mixture, propylene glycol monoethyl ether-propylene glycol methyl ether acetate mixture, ethylene glycol monoethyl ether-propylene glycol methyl ether acetate mixture, propylene glycol monopropyl ether-propylene glycol methyl ether acetate mixture, ethylene glycol monopropyl ether-propylene glycol methyl ether acetate mixture, etc. are preferable, but the combination is not limited to these.
The mixing ratio of the water-soluble organic solvent and the sparingly water-soluble organic solvent may be appropriately selected, and the water-soluble organic solvent is preferably 0.1 to 1,000 parts by mass, more preferably 1 to 500 parts by mass, and still more preferably 2 to 100 parts by mass, based on 100 parts by mass of the sparingly water-soluble organic solvent.
Then, the mixture may be washed with neutral water. The water may be deionized water or ultrapure water. The amount of the water is preferably 0.01 to 100L, more preferably 0.05 to 50L, and still more preferably 0.1 to 5L, based on 1L of the thermosetting silicon-containing material (Sx) solution. The washing may be carried out by filling the two into the same vessel, agitating and mixing them, and then leaving the vessel to stand and separating the aqueous layer. The number of washing times is preferably 1 to 5 times, but the washing effect is not obtained for a corresponding number of times even if washing is performed 10 times or more.
Other methods for removing the acid catalyst include a method using an ion exchange resin and a method of removing the acid catalyst by neutralizing the acid catalyst with an epoxy compound such as ethylene oxide or propylene oxide. The method can be appropriately selected in accordance with the acid catalyst used in the reaction.
Since a part of the thermosetting silicon-containing material (Sx) enters the water layer by the washing operation at this time, the washing frequency and the amount of the washing water can be appropriately selected in consideration of the catalyst removing effect and the classifying effect.
The solution of the thermosetting silicon-containing material (Sx) containing the acid catalyst remaining and the solution of the thermosetting silicon-containing material (Sx) from which the acid catalyst has been removed are both subjected to solvent exchange under reduced pressure with the addition of a final solvent, thereby obtaining a desired solution of the thermosetting silicon-containing material (Sx). The temperature of the solvent exchange depends on the kind of the reaction solvent and the extraction solvent to be removed, and is preferably 0 to 100 ℃, more preferably 10 to 90 ℃, and still more preferably 15 to 80 ℃. The degree of pressure reduction at this time varies depending on the kind of the extraction solvent to be removed, the exhaust device, the condensing device and the heating temperature, and is preferably not more than atmospheric pressure, more preferably not more than 80kPa, further preferably not more than 50 kPa.
In this case, the thermosetting silicon-containing material (Sx) may become unstable due to a change in the solvent. The reason is that, because of the compatibility between the final solvent and the thermosetting silicon-containing material (Sx), a monohydric or dihydric or higher alcohol having a cyclic ether as a substituent described in japanese patent application laid-open No. 2009-126940 (0181) to 0182) may be added as a stabilizer for prevention. The amount of the addition is preferably 0 to 25 parts by mass, more preferably 0 to 15 parts by mass, still more preferably 0 to 5 parts by mass, but more preferably 0.5 parts by mass or more per 100 parts by mass of the thermosetting silicon-containing material (Sx) in the solution before the solvent exchange. If necessary, a monohydric or dihydric or higher alcohol having a cyclic ether as a substituent may be added to the solution before the solvent exchange to perform the solvent exchange operation.
When the thermosetting silicon-containing material (Sx) is concentrated to a certain concentration or more, the condensation reaction proceeds further, and the material may be changed to a state incapable of being dissolved in the organic solvent, and therefore, it is preferable to be in a solution state with an appropriate concentration in advance. If the concentration of the solvent is too low, the amount of the solvent becomes too large, and it is preferable in terms of economy that the solution is obtained in a state of a moderate concentration. The concentration in this case is preferably 0.1 to 20 mass%.
The final solvent to be added to the solution of the thermosetting silicon-containing material (Sx) is preferably an alcohol-based solvent, and particularly a monoalkyl ether derivative such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, or butylene glycol. Specifically, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, diacetone alcohol and the like are preferable.
If the solvent is a main component, a non-alcohol solvent may be added as an auxiliary solvent. Examples of the auxiliary solvent include acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ -butyrolactone, methyl isobutyl ketone, and cyclopentyl methyl ether.
In another reaction operation using an acid catalyst, water or an aqueous organic solvent is added to the hydrolyzable monomer (Sm) or the organic solution of the hydrolyzable monomer (Sm) to start the hydrolysis reaction. In this case, the catalyst may be added to the hydrolyzable monomer (Sm) or to an organic solution of the hydrolyzable monomer (Sm), or may be added to water or a water-containing organic solvent. The reaction temperature is preferably 0 to 100 ℃, more preferably 10 to 80 ℃. When water is dropped, the temperature is heated to 10 to 50 ℃, and then the temperature is raised to 20 to 80 ℃ to be aged.
When an organic solvent is used, the water-soluble organic solvent is preferably used, and examples thereof include polyhydric alcohol condensate derivatives such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, butylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butylene glycol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butylene glycol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether and the like, and mixtures thereof.
The amount of the organic solvent to be used is preferably 0 to 1,000ml, more preferably 0 to 500ml, based on 1 mole of the hydrolyzable monomer (Sm). If the amount of the organic solvent used is not more than the upper limit, the reaction vessel is small and economical. The obtained reaction mixture is subjected to a post-treatment in the same manner as described above to obtain a thermosetting silicon-containing material (Sx).
[ Synthesis method of thermosetting silicon-containing Material (Sx) 2: base catalyst
The thermosetting silicon-containing material (Sx) can be produced by subjecting a mixture of 1 or 2 or more types of hydrolyzable monomers (Sm) to hydrolytic condensation in the presence of an alkali catalyst. Used at this timeExamples of the base catalyst include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, hexamethylenediamine, dimethylamine, diethylamine, ethylmethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, dicyclohexylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononene, diazabicycloundecene, hexamethylenetetramine, aniline, N-dimethylaniline, pyridine, N-dimethylaminopyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, tetramethylammonium hydroxide, choline hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide. The amount of the catalyst to be used is preferably 1X 10 mol based on 1 mol of the hydrolyzable monomer (Sm)-6Mol to 10 mol, preferably 1X 10 mol -5Mol to 5 mol, more preferably 1X 10 mol-4Mol to 1 mol.
The amount of water used in obtaining the thermosetting silicon-containing material (Sx) from the hydrolyzable monomer (Sm) by hydrolytic condensation is preferably 0.1 to 50 moles per 1 mole of the hydrolyzable substituent bonded to the hydrolyzable monomer (Sm). When the amount of water is 50 mol or less, the apparatus used for the reaction is small and economical.
In terms of the operation method, the hydrolyzable monomer (Sm) is added to the aqueous catalyst solution to initiate the hydrolytic condensation reaction. In this case, the organic solvent may be added to the aqueous catalyst solution, the hydrolyzable monomer (Sm) may be diluted with the organic solvent in advance, or both may be carried out. The reaction temperature is preferably 0 to 100 ℃, more preferably 5 to 80 ℃. The method of keeping the temperature at 5 to 80 ℃ and then curing at 20 to 80 ℃ is preferable when the hydrolyzable monomer (Sm) is dropped.
The organic solvent may be added to the aqueous alkali catalyst solution or the organic solvent capable of diluting the hydrolyzable monomer (Sm), and the same is preferably used as the organic solvent exemplified above which may be added to the aqueous acid catalyst solution. The amount of the organic solvent used is preferably 0 to 1,000ml per 1 mole of the hydrolyzable monomer (Sm) in order to allow the reaction to proceed economically.
Thereafter, if necessary, a neutralization reaction of the catalyst is carried out to obtain an aqueous reaction mixture solution. In this case, the amount of the acidic substance usable for neutralization is preferably 0.1 to 2 equivalents relative to the basic substance used for the catalyst. The acidic substance may be any substance as long as it is acidic in water.
Then, it is preferable to remove by-products such as alcohols generated by the hydrolytic condensation reaction from the reaction mixture by, for example, reducing the pressure. In this case, the temperature for heating the reaction mixture depends on the kind of the organic solvent added and the alcohol generated in the reaction, and is preferably 0 to 100 ℃, more preferably 10 to 90 ℃, and still more preferably 15 to 80 ℃. The degree of pressure reduction at this time varies depending on the kind of organic solvent, alcohol, etc. to be removed, the exhaust device, the condensing device, and the heating temperature, and is preferably not more than atmospheric pressure, more preferably not more than 80kPa, and still more preferably not more than 50 kPa. The amount of alcohol to be removed at this time is difficult to be precisely known, and it is preferable to remove about 80 mass% or more of the alcohol or the like produced.
Then, in order to remove the catalyst used for the hydrolysis and condensation, the thermosetting silicon-containing material (Sx) is extracted with an organic solvent. The organic solvent used in this case is preferably one capable of dissolving the thermosetting silicon-containing material (Sx) and separating into 2 layers when mixed with water. Such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, gamma-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, and the like, and mixtures thereof.
Then, in order to remove the alkali catalyst used for the hydrolysis and condensation, the thermosetting silicon-containing material (Sx) is extracted with an organic solvent. The organic solvent used in this case is preferably one which can dissolve the thermosetting silicon-containing material (Sx) and which separates into 2 layers when mixed with water. Mixtures of water-soluble organic solvents and sparingly water-soluble organic solvents may also be used.
Specific examples of the organic solvent used for removing the base catalyst include the same organic solvents as those specifically exemplified above for removing the acid catalyst, and mixtures of water-soluble organic solvents and sparingly water-soluble organic solvents.
The mixing ratio of the water-soluble organic solvent and the sparingly water-soluble organic solvent is appropriately selected, and the water-soluble organic solvent is preferably 0.1 to 1,000 parts by mass, more preferably 1 to 500 parts by mass, and still more preferably 2 to 100 parts by mass, based on 100 parts by mass of the sparingly water-soluble organic solvent.
Then washed with neutral water. The water is usually deionized water or ultrapure water. The amount of water is preferably 0.01 to 100L, more preferably 0.05 to 50L, and still more preferably 0.1 to 5L, based on 1L of the solution of the thermosetting silicon-containing material (Sx). The washing may be carried out by filling the two into the same vessel, agitating and mixing them, and then leaving the vessel to stand and separating the aqueous layer. The number of washing times is preferably 1 to 5 times, but the washing effect is not obtained for a corresponding number of times even if washing is performed 10 times or more.
The final solvent was added to the washed solution of the thermosetting silicon-containing material (Sx), and solvent exchange was performed under reduced pressure to obtain a desired solution of the thermosetting silicon-containing material (Sx). The temperature of the solvent exchange at this time depends on the kind of the extraction solvent to be removed, and is preferably 0 to 100 ℃, more preferably 10 to 90 ℃, and still more preferably 15 to 80 ℃. The degree of pressure reduction at this time varies depending on the kind of the extraction solvent to be removed, the exhaust device, the condensing device and the heating temperature, and is preferably not more than atmospheric pressure, more preferably not more than 80kPa, further preferably not more than 50 kPa.
The final solvent to be added to the solution of the thermosetting silicon-containing material (Sx) is preferably an alcohol-based solvent, and more preferably a monoalkyl ether of ethylene glycol, diethylene glycol, triethylene glycol, or the like, or a monoalkyl ether of propylene glycol, dipropylene glycol, or the like. Specifically, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, diacetone alcohol, and the like.
In another reaction operation using an alkali catalyst, water or a water-containing organic solvent is added to the hydrolyzable monomer (Sm) or an organic solution of the hydrolyzable monomer (Sm) to start the hydrolysis reaction. In this case, the catalyst may be added to the hydrolyzable monomer (Sm) or to an organic solution of the hydrolyzable monomer (Sm), or may be added to water or a water-containing organic solvent in advance. The reaction temperature is preferably 0 to 100 ℃, more preferably 10 to 80 ℃. When the water drops, the temperature is heated to 10-50 ℃, and then the temperature is raised to 20-80 ℃ and the mixture is cured.
The organic solvent which can be used as the organic solution or the water-containing organic solvent of the hydrolyzable monomer (Sm) is preferably water-soluble, and examples thereof include polyhydric alcohol condensate derivatives such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether and the like, and mixtures thereof.
The molecular weight of the thermosetting silicon-containing material (Sx) obtained by the above synthesis method 1 or 2 can be adjusted not only by the selection of the hydrolyzable monomer (Sm) but also by the control of the reaction conditions during polymerization, and if the weight average molecular weight is 100,000 or less, foreign matter and coating unevenness are not generated, so the weight average molecular weight is 100,000 or less, more preferably 200 to 50,000, further preferably 300 to 30,000. For the data of the weight average molecular weight, the molecular weight was represented in terms of polystyrene using Gel Permeation Chromatography (GPC) using RI as a detector and tetrahydrofuran as a dissolution solvent, using polystyrene as a standard substance.
The physical properties of the thermosetting silicon-containing material (Sx) used in the present invention vary depending on the kind of acid or base catalyst used in the hydrolytic condensation and the reaction conditions. Therefore, the properties of the resist underlayer film can be appropriately selected according to the purpose.
Further, a silicon-containing material derivative produced by mixing the hydrolyzable monomer (Sm) with a hydrolyzable metal compound represented by the general formula (Mm) below under the above-described conditions using an acid or base catalyst can be used as a component of the resist underlayer film forming composition.
U(OR7)m7(OR8)m8(Mm)
In the formula, R7、R8Is an organic group having 1 to 30 carbon atoms, m7+ m8 is the same number as the valence number determined by the type of U, m7 and m8 are integers of 0 or more, and U is an element of group III, group IV or group V of the periodic table and does not include carbon and silicon.
The hydrolyzable metal compound (Mm) used in this case is as follows. When U is boron, examples of the compound represented by the general formula (Mm) include boron methoxide, boron ethoxide, boron propoxide, boron butoxide, boron pentoxide, boron hexoxide, boron cyclopentoxide, boron cyclohexoxide, boron allyloxide, boron phenoxide, boron methoxyethoxide, boric acid, and boron oxide as monomers.
When U is aluminum, examples of the compound represented by the general formula (Mm) include aluminum methoxide, aluminum ethoxide, aluminum propoxide, aluminum butoxide, aluminum pentoxide, aluminum hexyloxide, aluminum cyclopentoxide, aluminum cyclohexyloxide, aluminum allyloxide, aluminum phenoxide, aluminum methoxyethoxide, aluminum ethoxyethoxide, aluminum dipropoxyethylacetoacetate, aluminum dibutoxyethylacetoacetate, aluminum propoxybietylacetoacetate, aluminum butoxybisethylacetoacetate, aluminum 2, 4-pentanedionate, and aluminum 2,2,6, 6-tetramethyl-3, 5-heptanedionate as monomers.
When U is gallium, examples of the compound represented by the general formula (Mm) include gallium methoxide, gallium ethoxide, gallium propoxide, gallium butoxide, gallium pentoxide, gallium hexoxide, gallium cyclopentoxide, gallium cyclohexoxide, gallium allyloxide, gallium phenoxide, gallium methoxyethoxide, gallium ethoxyethoxide, gallium dipropoxyethylacetoacetate, gallium dibutoxyethylacetoacetate, gallium propoxybietylacetoacetate, gallium butoxybisethylacetoacetate, gallium 2, 4-pentanedionate, gallium 2,2,6, 6-tetramethyl-3, 5-heptanedionate, and the like as monomers.
When U is yttrium, examples of the compound represented by the general formula (Mm) include yttrium methoxide, yttrium ethoxide, yttrium propoxide, yttrium butoxide, yttrium pentoxide, yttrium hexoxide, yttrium cyclopentoxide, yttrium cyclohexoxide, yttrium allyloxide, yttrium phenoxide, yttrium methoxyethoxide, yttrium ethoxyethoxide, yttrium dipropoxyethylacetoacetate, yttrium dibutoxyethylacetoacetate, yttrium propoxybietylacetoacetate, yttrium butoxybisethylacetoacetate, yttrium 2, 4-pentanedionate, yttrium 2,2,6, 6-tetramethyl-3, 5-heptanedionate and the like as monomers.
When U is germanium, examples of the compound represented by the general formula (Mm) include germanium methoxide, germanium ethoxide, germanium propoxide, germanium butoxide, germanium pentoxide, germanium hexyloxide, germanium cyclopentoxide, germanium cyclohexyloxide, germanium allyloxide, germanium phenoxide, germanium methoxyethoxide, germanium ethoxyethoxide, and the like.
When U is titanium, examples of the compound represented by the general formula (Mm) include titanium methoxide, titanium ethoxide, titanium propoxide, titanium butoxide, titanium pentoxide, titanium hexyloxide, titanium cyclopentoxide, titanium cyclohexyloxide, titanium allyloxide, titanium phenoxide, titanium methoxyethoxide, titanium ethoxyethoxide, titanium dipropoxybis-ethylacetoacetate, titanium dibutoxybis-ethylacetoacetate, titanium dipropoxybis-2, 4-pentanedionate, and titanium dibutoxybis-2, 4-pentanedionate as monomers.
When U is hafnium, examples of the compound represented by the general formula (Mm) include hafnium methoxide, hafnium ethoxide, hafnium propoxide, hafnium butoxide, hafnium pentoxide, hafnium hexoxide, hafnium cyclopentoxide, hafnium cyclohexoxide, hafnium allyloxide, hafnium phenoxide, hafnium methoxyethoxide, hafnium ethoxyethoxide, hafnium dipropoxybisetoethylacetoacetate, hafnium dibutoxybisetoacetoacetate, hafnium dipropoxybis 2, 4-pentanedionate, hafnium dibutoxybis 2, 4-pentanedionate, and the like as monomers.
When U is tin, examples of the compound represented by the general formula (Mm) include tin methoxide, tin ethoxide, tin propoxide, tin butoxide, tin phenoxide, tin methoxyethoxide, tin ethoxyethoxide, tin 2, 4-pentanedionate, and tin 2,2,6, 6-tetramethyl-3, 5-heptanedionate as monomers.
When U is arsenic, examples of the compound represented by the general formula (Mm) include arsenic methoxide, arsenic ethoxide, arsenic propoxide, arsenic butoxide, arsenic phenoxide and the like as monomers.
When U is antimony, examples of the compound represented by the general formula (Mm) include antimony methoxide, antimony ethoxide, antimony propoxide, antimony butoxide, antimony phenoxide, antimony acetate, and antimony propionate as monomers.
When U is niobium, examples of the compound represented by the general formula (Mm) include niobium methoxide, niobium ethoxide, niobium propoxide, niobium butoxide, niobium phenoxide and the like as monomers.
When U is tantalum, examples of the compound represented by the general formula (Mm) include tantalum methoxide, tantalum ethoxide, tantalum propoxide, tantalum butoxide, tantalum phenoxide, and the like as monomers.
When U is bismuth, examples of the compound represented by the general formula (Mm) include bismuth methoxide, bismuth ethoxide, bismuth propoxide, bismuth butoxide, bismuth phenoxide and the like as monomers.
When U is phosphorus, examples of the compound represented by the general formula (Mm) include trimethyl phosphite, triethyl phosphite, tripropyl phosphite, trimethyl phosphate, triethyl phosphate, tripropyl phosphate and phosphorus pentoxide as monomers.
When U is vanadium, examples of the compound represented by the general formula (Mm) include vanadium bis (2, 4-pentanedionate) oxide, vanadium 2, 4-pentanedionate, vanadium tributoxide oxide, vanadium tripropyloxide and the like as monomers.
When U is zirconium, examples of the compound represented by the general formula (Mm) include zirconium methoxide, zirconium ethoxide, zirconium propoxide, zirconium butoxide, zirconium phenoxide, bis (2, 4-pentanedionate) zirconium dibutoxide, bis (2,2,6, 6-tetramethyl-3, 5-heptanedionate) zirconium dipropoxide, and the like as monomers.
< method for measuring diffusion distance of curing catalyst (Xc) >
The curing catalyst (Xc) of the present invention has a diffusion distance of 5nm or less from a resist underlayer film formed from a resist underlayer film forming composition containing silicon to a curing catalyst (Xc) of a resist overlayer film formed on the resist underlayer film. The diffusion distance of the curing catalyst (Xc) is described below with reference to the drawings.
Fig. 1 is a flowchart showing a step of gradually diffusing the curing catalyst (Xc) from the silicon-containing resist underlayer film in order to measure the diffusion distance of the curing catalyst (Xc) of the present invention. First, a silicon-containing resist underlayer film forming composition containing a curing catalyst (Xc) is spin-coated (spin-coated) on a substrate 1, and a silicon-containing resist underlayer film 2 is formed by heat treatment (fig. 1 (b)). The silicon-containing resist underlayer film forming composition is heated and cured so as not to be mixed with the upper layer resist film 3 formed on the film. In this curing, the silanol group and the alkoxysilane group of the thermosetting silicon-containing material (Sx) contained in the composition for forming a silicon-containing resist underlayer film undergo dehydration reaction and dealcoholization reaction, and a siloxane bond is newly formed. The curing catalyst (Xc) is added to accelerate the reaction. Thereby, the hardening of the silicon-containing resist underlayer film 2 proceeds sufficiently, and the solvent-insoluble silicon-containing resist underlayer film 2 is obtained. On the cured silicon-containing resist underlayer film 2, a composition containing a resin used for a so-called photosensitive resist composition (for example, a resin in which a functional group imparting alkali solubility in an alkali-soluble resin having a hydroxyl group or a carboxyl group as a partial structure is protected with an acid-releasing group) and an acid generator generating acid by a high-energy ray is spin-coated and heated to form an organic resist underlayer film 3. The heating temperature in this case is not particularly limited as long as the solvent in the resist upper layer film forming composition is volatilized, and is preferably 50 ℃ to 300 ℃, more preferably 70 ℃ to 200 ℃ (fig. 1 (c)). Then, high-energy rays are irradiated to decompose the acid generator. The high-energy ray is generated by selecting high-pressure mercury lamp light, KrF excimer laser, ArF excimer laser, other appropriate light source, and energy line source. The irradiation dose of the high-energy ray is preferably 1mJ to 1000mJ, more preferably 5mJ to 100mJ (FIG. 1 (d)). Then, in order to exhibit the alkali solubility of the resin, a heat treatment is performed to release the protecting group of the alkali-soluble functional group. The heat treatment temperature is preferably 50 ℃ to 250 ℃ inclusive, more preferably 70 ℃ to 200 ℃ inclusive. At this time, when the curing catalyst (Xc) diffuses from the silicon-containing resist underlayer film 2, the generated acid is neutralized by the curing catalyst (Xc), and a portion in which the alkali solubility of the resin is suppressed appears in the vicinity of the silicon-containing resist underlayer film 2 (fig. 1 (e)). When this is developed with an alkali developing solution, the portion from which the protecting group has been removed is dissolved in the developing solution, and the organic film resist upper layer film 4 remains in the vicinity of the silicon-containing resist lower layer film 2 in accordance with the diffusion distance of the curing catalyst (Xc) (fig. 1 (f)). The thickness of the residual resist upper layer film 4 measured by the film thickness meter can be regarded as the diffusion distance of the curing catalyst (Xc) contained in the silicon-containing resist lower layer film 2. The curing catalyst (Xc) of the present invention has a diffusion distance of 5nm or less.
[ hardening catalyst (Xc) ]
Specific examples of the curing catalyst (Xc) include compounds represented by the following general formula (Xc 0).
LaHbA (Xc0)
Wherein L is lithium, sodium, potassium, rubidium, cesium, sulfonium, iodonium, phosphonium, or ammonium, A is a non-nucleophilic counter ion, a is an integer of 1 or more, b is 0 or an integer of 1 or more, and a + b is the valence number of the non-nucleophilic counter ion.
Specific examples of (Xc0) include a sulfonium salt of the following general formula (Xc-1), an iodonium salt of (Xc-2), a phosphonium salt of (Xc-3), an ammonium salt of (Xc-4), and an alkali metal salt.
Sulfonium salt (Xc-1), iodonium salt (Xc-2), and phosphonium salt (Xc-3) are listed below.
[ solution 7]
Figure BDA0002465657770000261
Further, the ammonium salt (Xc-4) can be exemplified as follows.
[ solution 8]
Figure BDA0002465657770000262
In the formula, R204、R205、R206、R207Each represents a C1-12 linear, branched or cyclic alkyl, alkenyl, oxoalkyl or oxoalkenyl group, or a C6-20 substituted alkyl or oxoalkenyl groupOr an unsubstituted aryl group, an aralkyl group having 7 to 12 carbon atoms or an aryloxyalkyl group, wherein a part or all of the hydrogen atoms of the above groups may be substituted with an alkoxy group. And R is205And R206Or form a ring, when R forms a ring205、R206Each represents an alkylene group having 1 to 6 carbon atoms. A. the-Denotes a non-nucleophilic counter ion. R208、R209、R210、R211And R204、R205、R206、R207Likewise, it may be a hydrogen atom. R208And R209、R208And R209And R210Or form a ring, when R forms a ring 208And R209And R208And R209And R210Represents an alkylene group having 3 to 10 carbon atoms.
R is as defined above204、R205、R206、R207、R208、R209、R210、R211Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopropylmethyl group, a 4-methylcyclohexyl group, a cyclohexylmethyl group, a norbornyl group, and an adamantyl group. Examples of the alkenyl group include vinyl, allyl, propenyl, butenyl, hexenyl, and cyclohexenyl. Examples of the oxoalkyl group include a 2-oxocyclopentyl group and a 2-oxocyclohexyl group, and also include a 2-oxopropyl group, a 2-cyclopentyl-2-oxoethyl group, a 2-cyclohexyl-2-oxoethyl group, and a 2- (4-methylcyclohexyl) -2-oxoethyl group. Examples of the aryl group include phenyl groups, naphthyl groups, and the like, and alkoxyphenyl groups such as p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-t-butoxyphenyl and m-t-butoxyphenyl groups, alkylphenyl groups such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-t-butylphenyl, 4-butylphenyl and dimethylphenyl groups, alkylnaphthyl groups such as methylnaphthyl and ethylnaphthyl groups, alkoxynaphthyl groups such as methoxynaphthyl and ethoxynaphthyl groups, dialkylnaphthyl groups such as dimethylnaphthyl and diethylnaphthyl groups, dialkoxynaphthyl groups such as dimethoxynaphthyl and diethoxynaphthyl groups, and the like. Aralkyl radical Examples of the group include benzyl, phenylethyl and phenethyl. Examples of the aryloxyalkyl group include a 2-aryl-2-oxoethyl group such as a 2-phenyl-2-oxoethyl group, a 2- (1-naphthyl) -2-oxoethyl group, and a 2- (2-naphthyl) -2-oxoethyl group.
As A-Examples of the non-nucleophilic counter ion include hydroxy acid ion, formic acid ion, acetic acid ion, propionic acid ion, butyric acid ion, valeric acid ion, caproic acid ion, heptanoic acid ion, caprylic acid ion, pelargonic acid ion, capric acid ion, oleic acid ion, stearic acid ion, linoleic acid ion, linolenic acid ion, benzoic acid ion, phthalic acid ion, isophthalic acid ion, terephthalic acid ion, salicylic acid ion, trifluoroacetic acid ion, monochloroacetic acid ion, dichloroacetic acid ion, trichloroacetic acid ion, fluorine ion, chlorine ion, bromine ion, iodine ion, nitric acid ion, nitrous acid ion, chloric acid ion, bromic acid ion, methanesulfonic acid ion, p-toluenesulfonic acid ion, monomethylsulfuric acid ion and other ions having a valence of 1 st, oxalic acid ion having a valence of 1 or 2, malonic acid ion, methylmalonic acid ion, ethylmalonic acid ion, propylmalonic acid ion, and the like, Butylmalonate ion, dimethylmalonate ion, diethylmalonate ion, succinate ion, methylsuccinate ion, glutarate ion, adipate ion, itaconate ion, maleate ion, fumarate ion, citraconate ion, citrate ion, carbonate ion, sulfate ion, and the like.
Examples of the alkali metal salt include lithium, sodium, potassium, cesium hydroxy acid salts, formate salts, acetate salts, propionate salts, butyrate salts, valeric acid salts, hexanoic acid salts, heptanoic acid salts, octanoic acid salts, nonanoic acid salts, decanoic acid salts, oleic acid salts, stearic acid salts, linolic acid salts, benzoic acid salts, phthalic acid salts, isophthalic acid salts, terephthalic acid salts, salicylic acid salts, trifluoroacetic acid salts, monochloroacetic acid salts, dichloroacetic acid salts, trichloroacetic acid salts and the like 1-valent salts, 1-valent or 2-valent oxalic acid salts, malonic acid salts, methylmalonic acid salts, ethylmalonic acid salts, propylmalonic acid salts, butylmalonic acid salts, dimethylmalonic acid salts, diethylmalonic acid salts, succinic acid salts, methylsuccinic acid salts, glutaric acid salts, adipic acid salts, itaconic acid salts, maleic acid salts, fumaric acid salts, citraconic salts, citric acid salts, carbonate salts.
Specifically, sulfonium salt (Xc-1) includes triphenylsulfonium formate, triphenylsulfonium acetate, triphenylsulfonium propionate, triphenylsulfonium butyrate, triphenylsulfonium benzoate, triphenylsulfonium phthalate, triphenylsulfonium isophthalate, triphenylsulfonium terephthalate, triphenylsulfonium salicylate, triphenylsulfonium triflate, triphenylsulfonium trifluoroacetate, triphenylsulfonium monochloroacetate, triphenylsulfonium dichloroacetate, triphenylsulfonium trichloroacetate, triphenylsulfonium hydroxide, triphenylsulfonium nitrate, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium oxalate, triphenylsulfonium malonate, triphenylsulfonium methylmalonate, triphenylsulfonium ethylmalonate, triphenylsulfonium propylmalonate, triphenylsulfonium butylmalonate, triphenylsulfonium dimethylmalonate, triphenylsulfonium diethylmalonate, triphenylsulfonium succinate, triphenylsulfonium methylsuccinate, triphenylsulfonium methyl succinate, triphenylsulfonium propionate, triphenylsulfonium acetate, triphenylsulfonium benzoate, triphenylsulfonium hydrogen chloride, triphenylsulfonium bromide, triphenylsulfonium oxalate, triphenylsulfonium hydrogen malonate, triphenylsulfonium hydrogen chloride, triphenylsulfonium hydrogen, Glutaric acid triphenyl sulfonium, adipic acid triphenyl sulfonium, itaconic acid triphenyl sulfonium, maleic acid triphenyl sulfonium, fumaric acid triphenyl sulfonium, citraconic acid triphenyl sulfonium, citric acid triphenyl sulfonium, carbonic acid triphenyl sulfonium, oxalic acid bis triphenyl sulfonium, maleic acid bis triphenyl sulfonium, fumaric acid bis triphenyl sulfonium, citraconic acid bis triphenyl sulfonium, citric acid bis triphenyl sulfonium, carbonic acid bis triphenyl sulfonium, and the like.
Also, specific example of a salt (Xc-2) can be diphenyliodonium formate, diphenyliodonium acetate, diphenyliodonium propionate, diphenyliodonium butyrate, diphenyliodonium benzoate, diphenyliodonium phthalate, diphenyliodonium isophthalate, diphenyliodonium terephthalate, diphenyliodonium salicylate, diphenyliodonium triflate, diphenyliodonium trifluoroacetate, diphenyliodonium monochloroacetate, diphenyliodonium dichloroacetate, diphenyliodonium trichloroacetate, diphenyliodonium hydroxide, diphenyliodonium nitrate, diphenyliodonium chloride, diphenyliodonium bromide, diphenyliodonium iodide, diphenyliodonium oxalate, diphenyliodonium maleate, diphenyliodonium fumarate, iodonium fumarate, diphenyliodonium fumarate, citraconic acid, diphenyliodonium, citraconic acid diphenyliodonium, diphenyliodonium citrate, diphenyliodonium carbonate, diphenyliodonium oxalate, diphenyliodonium maleate, diphenyliodonium fumarate, iodonium methacrylate, diphenyliodonium, iodonium citrate, and iodonium, Bisdiphenyliodonium carbonate, and the like.
Specific examples of the phosphonium salt (Xc-3) include tetraethylphosphonium formate, tetraethylphosphonium acetate, tetraethylphosphonium propionate, tetraethylphosphonium butyrate, tetraethylphosphonium benzoate, tetraethylphosphonium phthalate, tetraethylphosphonium isophthalate, tetraethylphosphonium terephthalate, tetraethylphosphonium salicylate, tetraethylphosphonium trifluoromethanesulfonate, tetraethylphosphonium trifluoroacetate, tetraethylphosphonium monochloroacetate, tetraethylphosphonium dichloroacetate, tetraethylphosphonium trichloroacetate, tetraethylphosphonium hydroxide, tetraethylphosphonium nitrate, tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetraethylphosphonium iodide, tetraethylphosphonium oxalate, tetraethylphosphonium maleate, tetraethylphosphonium fumarate, tetraethylphosphonium citraconate, tetraethylphosphonium citrate, tetraethylphosphonium carbonate, bistetraethylammonium oxalate, bistetraethylphosphonium maleate, bistetraethylphosphonium fumarate, bistetraethylphosphonium citrate, and, Bis-tetraethylphosphonium carbonate, tetraphenylphosphonium formate, tetraphenylphosphonium acetate, tetraphenylphosphonium propionate, tetraphenylphosphonium butyrate, tetraphenylphosphonium benzoate, tetraphenylphosphonium phthalate, tetraphenylphosphonium isophthalate, tetraphenylphosphonium terephthalate, tetraphenylphosphonium salicylate, tetraphenylphosphonium trifluoromethanesulfonate, tetraphenylphosphonium trifluoroacetate, tetraphenylphosphonium monochloroacetate, tetraphenylphosphonium dichloroacetate, tetraphenylphosphonium trichloroacetate, tetraphenylphosphonium hydroxide, tetraphenylphosphonium nitrate, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, tetraphenylphosphonium oxalate, tetraphenylphosphonium maleate, tetraphenylphosphonium fumarate, tetraphenylphosphonium citraconate, tetraphenylphosphonium citrate, tetraphenylphosphonium carbonate, bis tetraphenylphosphonium oxalate, bis tetraphenylphosphonium maleate, bis tetraphenylphosphonium fumarate, bis tetraphenylphosphonium citraconate, bis tetraphenylphosphonium citrate, bis tetraphenylphosphonium carbonate, and the like.
On the other hand, specific examples of the ammonium salt (Xc-4) include tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butyrate, tetramethylammonium benzoate, tetramethylammonium phthalate, tetramethylammonium isophthalate, tetramethylammonium terephthalate, tetramethylammonium salicylate, tetramethylammonium trifluoromethanesulfonate, tetramethylammonium trifluoroacetate, tetramethylammonium monochloroacetate, tetramethylammonium dichloroacetate, tetramethylammonium trichloroacetate, tetramethylammonium hydroxide, tetramethylammonium nitrate, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium monomethylsulfate, tetramethylammonium oxalate, tetramethylammonium malonate, tetramethylammonium maleate, tetramethylammonium fumarate, tetramethylammonium citraconate, tetramethylammonium citrate, tetramethylammonium carbonate, bistetramethylammonium oxalate, bistetramethylammonium malonate, bis-tetramethylammonium citrate, bis-tetramethylammonium hydrogen-acetate, bis-tetramethylammonium hydrogen-chloride, bis-tetramethylammonium hydrogen-sulfonate, bis-, Bis-tetramethylammonium maleate, bis-tetramethylammonium fumarate, bis-tetramethylammonium citraconate, bis-tetramethylammonium citrate, bis-tetramethylammonium carbonate, tetraethylammonium formate, tetraethylammonium acetate, tetraethylammonium propionate, tetraethylammonium butyrate, tetraethylammonium benzoate, tetraethylammonium phthalate, tetraethylammonium isophthalate, tetraethylammonium terephthalate, tetraethylammonium salicylate, tetraethylammonium triflate, tetraethylammonium trifluoroacetate, tetraethylammonium monochloroacetate, tetraethylammonium dichloroacetate, tetraethylammonium trichloroacetate, tetraethylammonium hydroxide, tetraethylammonium nitrate, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetraethylammonium monomethylsulfate, tetraethylammonium oxalate, tetraethylammonium malonate, tetraethylammonium maleate, tetraethylammonium fumarate, tetraethylammonium citraconate, tetraethylammonium citrate, Tetraethylammonium carbonate, bistetraethylammonium oxalate, bistetraethylammonium malonate, bistetraethylammonium maleate, bistetraethylammonium fumarate, bistetraethylammonium citraconate, bistetraethylammonium citrate, bistetraethylammonium carbonate, tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium propionate, tetrapropylammonium butyrate, tetrapropylammonium benzoate, tetrapropylammonium phthalate, tetrapropylammonium isophthalate, tetrapropylammonium terephthalate, tetrapropylammonium salicylate, tetrapropylammonium triflate, tetrapropylammonium trifluoroacetate, tetrapropylammonium monochloroacetate, tetrapropylammonium dichloroacetate, tetrapropylammonium trichloroacetate, tetrapropylammonium hydroxide, tetrapropylammonium nitrate, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium iodide, tetrapropylammonium monomethylsulfate, tetrapropylammonium oxalate, tetrapropylammonium malonate, tetrapropylammonium maleate, Tetrapropylammonium fumarate, tetrapropylammonium citraconate, tetrapropylammonium citrate, tetrapropylammonium carbonate, bistetrapropylammonium oxalate, bistetrapropylammonium malonate, bistetrapropylammonium maleate, bistetrapropylammonium fumarate, bistetrapropylammonium citraconate, bistetrapropylammonium citrate, bistetrapropylammonium carbonate, tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butyrate, tetrabutylammonium benzoate, tetrabutylammonium phthalate, tetrabutylammonium isophthalate, tetrabutylammonium terephthalate, tetrabutylammonium salicylate, tetrabutylammonium trifluoromethanesulfonate, tetrabutylammonium trifluoroacetate, tetrabutylammonium monochloroacetate, tetrabutylammonium dichloroacetate, tetrabutylammonium trichloroacetate, tetrabutylammonium hydroxide, tetrabutylammonium nitrate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium methanesulfonate, tetrabutylammonium monomethylsulfate, tetrabutylammonium monochloroacetate, tetrabutylammonium sulfate, ammonium sulfate, tetrabutylammonium sulfate, ammonium sulfate, Tetrabutylammonium oxalate, tetrabutylammonium malonate, tetrabutylammonium maleate, tetrabutylammonium fumarate, tetrabutylammonium citraconate, tetrabutylammonium citrate, tetrabutylammonium carbonate, trimethylphenylammonium formate, trimethylphenylammonium acetate, trimethylphenylammonium propionate, trimethylphenylammonium butyrate, trimethylphenylammonium benzoate, trimethylphenylammonium phthalate, trimethylphenylammonium isophthalate, trimethylphenylammonium terephthalate, trimethylphenylammonium salicylate, trimethylphenylammonium trifluoromethanesulfonate, trimethylphenylammonium trifluoroacetate, trimethylphenylammonium monochloroacetate, trimethylphenylammonium dichloroacetate, trimethylphenylammonium trichloroacetate, tetrabutylammonium citraconate, tetrabutylammonium citrate, tetrabutylammonium hydrogen carbonate, ammonium hydrogen carbonate, trimethylammonium propionate, trimethylammonium butyrate, trimethylphenylammonium benzoate, trimethylphenylammonium phthalate, trimethylphenyl, Trimethylphenylammonium hydroxide, trimethylphenylammonium nitrate, trimethylphenylammonium chloride, trimethylphenylammonium bromide, trimethylphenylammonium iodide, trimethylphenylammonium methanesulfonate, trimethylphenylammonium monomethylsulfate, trimethylphenylammonium oxalate, trimethylphenylammonium malonate, trimethylphenylammonium maleate, trimethylphenylammonium fumarate, trimethylphenylammonium citraconate, trimethylphenylammonium citrate, trimethylphenylammonium carbonate, bistrimethylphenylammonium oxalate, bistrimethylphenylammonium malonate, bistrimethylphenylammonium maleate, bistrimethylphenylammonium fumarate, bistrimethylphenylammonium citraconate, bistrimethylphenylammonium citrate, bistrimethylphenylammonium carbonate, triethylphenylammonium formate, triethylphenylammonium acetate, triethylphenylammonium propionate, triethylphenylammonium butyrate, triethylphenylammonium benzoate, tetramethylphenylammonium hydrogen chloride, trimethylphenylammonium maleate, trimethylphenyla, Triethylphenylammonium phthalate, triethylphenylammonium isophthalate, triethylphenylammonium terephthalate, triethylphenylammonium salicylate, triethylphenylammonium trifluoromethanesulfonate, triethylphenylammonium trifluoroacetate, triethylphenylammonium monochloroacetate, triethylphenylammonium dichloroacetate, triethylphenylammonium trichloroacetate, triethylphenylammonium hydroxide, triethylphenylammonium nitrate, triethylphenylammonium chloride, triethylphenylammonium bromide, triethylphenylammonium iodide, triethylphenylammonium methanesulfonate, triethylphenylammonium monomethylsulfate, triethylphenylammonium oxalate, triethylphenylammonium malonate, triethylphenylammonium maleate, triethylphenylammonium fumarate, triethylphenylammonium citraconate, triethylphenylammonium citrate, triethylphenylammonium carbonate, bistriethylphenylammonium oxalate, bistriethylphenylammonium malonate, triethylphenylammonium malonate, ammonium maleate, triethylphenylammonium fumarate, triethylphenylammonium citrate, triethylphenylammonium carbonate, bistrieylphenylammonium oxalate, bistrieylphenylammonium malonate, and the like, Bistrieylphenylammonium maleate, bistrieylphenylammonium fumarate, bistrieylphenylammonium citraconate, bistrieylphenylammonium citrate, bistrieylphenylammonium carbonate, benzyldimethylphenylammonium formate, benzyldimethylphenylammonium acetate, benzyldimethylphenylammonium propionate, benzyldimethylphenylammonium butyrate, benzyldimethylphenylammonium benzoate, benzyldimethylphenylammonium phthalate, benzyldimethylphenylammonium isophthalate, benzyldimethylphenylammonium terephthalate, benzyldimethylphenylammonium salicylate, benzyldimethylphenylammonium trifluoromethanesulfonate, benzyldimethylphenylammonium trifluoroacetate, benzyldimethylphenylammonium monochloroacetate, benzyldimethylphenylammonium dichloroacetate, benzyldimethylphenylammonium trichloroacetate, benzyldimethylphenylammonium hydroxide, benzyldimethylphenylammonium nitrate, benzyldimethylphenylammonium chloride, benzyldimethylphenylammonium bromide, benzyldimethylphenylammonium iodide, benzyldimethylphenylammonium methanesulfonate, benzyldimethylphenylammonium monomethylsulfate, benzyldimethylphenylammonium oxalate, benzyldimethylphenylammonium malonate, benzyldimethylphenylammonium maleate, benzyldimethylphenylammonium fumarate, benzyldimethylphenylammonium citraconate, benzyldimethylphenylammonium citrate, benzyldimethylphenylammonium carbonate, dibenzyldimethylphenylammonium oxalate, dibenzyldimethylphenylammonium malonate, dibenzyldimethylphenylammonium maleate, dibenzyldimethylphenylammonium fumarate, dibenzyldimethylphenylammonium citraconate, dibenzyldimethylphenylammonium citrate, dibenzyldimethylphenylammonium carbonate, and the like.
Examples of the alkali metal salt include lithium formate, lithium acetate, lithium propionate, lithium butyrate, lithium benzoate, lithium phthalate, lithium isophthalate, lithium terephthalate, lithium salicylate, lithium trifluoromethanesulfonate, lithium trifluoroacetate, lithium monochloroacetate, lithium dichloroacetate, lithium trichloroacetate, lithium hydroxide, lithium nitrate, lithium chloride, lithium bromide, lithium iodide, lithium methanesulfonate, lithium hydrogen oxalate, lithium hydrogen malonate, lithium hydrogen maleate, lithium hydrogen fumarate, lithium hydrogen citraconate, lithium hydrogen citrate, lithium hydrogen carbonate, lithium oxalate, lithium malonate, lithium maleate, lithium fumarate, lithium conate, lithium citrate, lithium carbonate, sodium formate, sodium acetate, sodium propionate, sodium butyrate, sodium benzoate, sodium phthalate, sodium isophthalate, sodium terephthalate, sodium salicylate, sodium trifluoromethanesulfonate, sodium trifluoroacetate, sodium monochloroacetate, sodium dichloroacetate, sodium trichloroacetate, Sodium hydroxide, sodium nitrate, sodium chloride, sodium bromide, sodium iodide, sodium methanesulfonate, sodium hydrogen oxalate, sodium hydrogen malonate, sodium hydrogen maleate, sodium hydrogen fumarate, sodium citraconate, sodium hydrogen citrate, sodium bicarbonate, sodium oxalate, sodium malonate, sodium maleate, sodium fumarate, sodium citraconate, sodium citrate, sodium carbonate, potassium formate, potassium acetate, potassium propionate, potassium butyrate, potassium benzoate, potassium phthalate, potassium isophthalate, potassium terephthalate, potassium salicylate, potassium trifluoromethanesulfonate, potassium trifluoroacetate, potassium monochloroacetate, potassium dichloroacetate, potassium trichloroacetate, potassium hydroxide, potassium nitrate, potassium chloride, potassium bromide, potassium iodide, potassium methanesulfonate, potassium hydrogen oxalate, potassium hydrogen malonate, potassium hydrogen maleate, potassium hydrogen fumarate, potassium citraconate, potassium hydrogen citrate, potassium hydrogen bicarbonate, potassium oxalate, potassium malonate, potassium maleate, Potassium fumarate, potassium citraconate, potassium citrate, potassium carbonate, and the like.
In the present invention, examples of the curing catalyst (Xc) include thermosetting polysiloxane (Xc-10) having a partial structure including an ammonium salt, a sulfonium salt, a phosphonium salt, and an iodonium salt.
As the raw material for producing (Xc-10) used herein, a compound represented by the following general formula (Xm) can be used.
R1A A1R2A A2R3A A3Si(OR0A)(4-A1-A2-A3)(Xm)
In the formula, R0AIs a C1-6 hydrocarbon group, R1A、R2A、R3AAt least one of the groups is an organic group having an ammonium salt, sulfonium salt, phosphonium salt, or iodonium salt, and the remainder is a hydrogen atom or a 1-valent organic group having 1 to 30 carbon atoms. A1, A2 and A3 are 0 or 1, and 1 is more than or equal to A1+ A2+ A3 is more than or equal to 3.
Xm is a hydrolyzable silicon compound having a sulfonium salt in a part of its structure, and the following general formula (Xm-1) is exemplified.
[ solution 9]
Figure BDA0002465657770000331
In the formula, RSA1、RSA2Each represents a C1-20 linear, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group, a C6-20 substituted or unsubstituted aryl group, or a C7-20 aralkyl or aryloxyalkyl group, and some or all of the hydrogen atoms of the above groups may be substituted with a 1-valent organic group such as alkoxy group, amino group, alkylamino group, halogen atom, or the like. And R isSA1And RSA2Or may form a ring together with the sulfur atom to which they are bonded, when R forms a ringSA1、RSA2Each represents an alkylene group having 1 to 6 carbon atoms. RSA3Is a linear, branched or cyclic alkylene group, alkenylene group or substituted or unsubstituted arylene group having 1 to 20 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with a 2-valent organic group such as alkoxy, amino or alkylamino.
In the general formula (Xm-1), (Si) is described for showing a bond site with Si.
Is X-As the ionic liquid, there may be mentioned hydroxy acid ion, fluorine ion, chlorine ion, bromine ion, iodine ion, formic acid ion, acetic acid ion, propionic acid ion, butyric acid ion, valeric acid ion, caproic acid ion, enanthic acid ion, caprylic acid ion, pelargonic acid ion, capric acid ion, oleic acid ion, stearic acid ion, linoleic acid ion, linolenic acid ion, benzoic acid ion, p-toluic acid ion, p-tert-butylbenzoic acid ion, phthalic acid ion, isophthalic acid ion, terephthalic acid ion, salicylic acid ion, trifluoroacetic acid ion, monochloroacetic acid ion, dichloroacetic acid ion, trichloroacetic acid ion, nitric acid ion, chloric acid ion, perchloric acid ion, bromic acid ion, iodic acid ion, methanesulfonic acid ion, benzenesulfonic acid ion, toluenesulfonic acid ion, monomethylsulfuric acid ion, hydrogen sulfate ion, oxalic acid ion, malonic acid ion, methylmalonic acid ion, Ethylmalonic acid ion, propylmalonic acid ion, butylmalonic acid ion, dimethylmalonic acid ion, diethylmalonic acid ion, succinic acid ion, methylsuccinic acid ion, glutaric acid ion, adipic acid ion, itaconic acid ion, maleic acid ion, fumaric acid ion, citraconic acid ion, citric acid ion, carbonic acid ion, and the like.
The cation moiety of the compound represented by the above general formula (Xm-1) includes the following ions.
[ solution 10]
Figure BDA0002465657770000341
For example, an example of the hydrolyzable silicon compound having an iodonium salt in a part of its structure is represented by the following general formula (Xm-2).
[ solution 11]
Figure BDA0002465657770000351
In the formula, RIA1Represents a linear, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxyalkyl group having 7 to 20 carbon atoms,and some or all of the hydrogen atoms of these groups may be substituted with 1-valent organic groups such as alkoxy groups, amino groups, alkylamino groups, halogen atoms, and the like. RIA2Is a linear, branched or cyclic alkylene group, alkenylene group or substituted or unsubstituted arylene group having 1 to 20 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with a 2-valent organic group such as alkoxy, amino or alkylamino.
In the above general formula (Xm-2), (Si) is described for the purpose of expressing the bond site with Si. X-As described above.
The cationic moiety of the compound represented by the general formula (Xm-2) includes the following ions.
[ solution 12]
Figure BDA0002465657770000352
For example: examples of hydrolyzable silicon compounds having a phosphonium salt in part of their structure include the following general formula (Xm-3).
[ solution 13]
Figure BDA0002465657770000361
In the formula, RPA1、RPA2、RPA3Each represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or an aryloxyalkyl group having 7 to 20 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted by an alkoxy group, an amino group, an alkylamino group, a halogen atom or the like. And R isPA1And RPA2Or may form a ring together with the phosphorus atom to which they are bonded, when R forms a ringPA1、RPA2Each represents an alkylene group having 1 to 6 carbon atoms. RPA4Is a C1-20 linear, branched or cyclic alkylene, alkenylene, C6-20 substituted or unsubstituted arylene, and some or all of the hydrogen atoms of the above groups may be substituted by alkoxy, amino, or alkaneAmino groups, and the like.
In the above general formula (Xm-3), (Si) is described for the purpose of expressing the bond site with Si. X-As described above.
The cationic moiety of the compound represented by the general formula (Xm-3) includes the following ions.
[ solution 14]
Figure BDA0002465657770000371
[ solution 15]
Figure BDA0002465657770000372
Examples of the hydrolyzable silicon compound having an ammonium salt in a part of its structure include the following general formula (Xm-4).
[ solution 16]
Figure BDA0002465657770000381
In the formula, RNA1、RNA2、RNA3Each represents hydrogen, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, an aralkyl group or an aryloxyalkyl group having 7 to 20 carbon atoms, and a part or all of hydrogen atoms of the above groups may be substituted with a 1-valent organic group such as an alkoxy group, an amino group or an alkylamino group. And R is NA1And RNA2Or may form a ring together with the nitrogen atom to which they are bonded, when R forms a ringNA1、RNA2Each represents an alkylene group having 1 to 6 carbon atoms, a nitrogen-containing cyclic heterocycle, or an aromatic heterocycle. RNA4Represents a C1-20 linear, branched or cyclic alkylene group, alkenylene group, C6-20 substituted or unsubstituted arylene group, and some or all of the hydrogen atoms of these groups may be substituted with a 2-valent organic group such as alkoxy, amino, alkylamino, etc., R isNA1And RNA2、RNA1And RNA4Form a ring structure and further containWhen there is no saturated nitrogen, nN3When not more than 0, nN3＝1。
In the above general formula (Xm-4), (Si) is described for the purpose of expressing the bond site with Si. X-As described above.
The cationic moiety of the compound represented by the general formula (Xm-4) includes the following ions.
[ solution 17]
Figure BDA0002465657770000391
[ solution 18]
Figure BDA0002465657770000401
[ solution 19]
Figure BDA0002465657770000411
[ solution 20]
Figure BDA0002465657770000421
[ solution 21]
Figure BDA0002465657770000431
[ solution 22]
Figure BDA0002465657770000441
[ solution 23]
Figure BDA0002465657770000451
(organic solvent)
The silicon-containing resist underlayer film forming composition of the present invention contains a solvent. The solvent is preferably an alcohol solvent, and more preferably a monoalkyl ether derivative such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, or butylene glycol. Specifically, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether and the like are preferable.
If the solvent is a main component, a non-alcohol solvent may be added as an auxiliary solvent. Examples of the auxiliary solvent include acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ -butyrolactone, methyl isobutyl ketone, and cyclopentyl methyl ether.
(Water)
Water may be added to the silicon-containing resist underlayer film forming composition of the present invention. When water is added, the polysiloxane compound in the composition is hydrated, and the lithographic performance is improved. The content of water in the solvent component of the composition for forming a silicon-containing resist underlayer film of the present invention is preferably more than 0 mass% and less than 50 mass%, more preferably 0.3 to 30 mass%, and still more preferably 0.5 to 20 mass%. If the water content is less than 50 mass%, the uniformity of the silicon-containing resist underlayer film is good and no pinholes (eyeholes) are formed.
(high boiling point solvent)
The silicon-containing resist underlayer film forming composition of the present invention may contain a high boiling point solvent having a boiling point of 180 degrees or higher, if necessary. As the high boiling point solvent, 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1, 2-propanediol, 1, 3-butanediol, 2, 4-pentanediol, 2-methyl-2, 4-pentanediol, 2, 5-hexanediol, 2, 4-heptanediol, 2-ethyl-1, 3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, gamma-butyrolactone, tripropylene glycol monomethyl ether, diacetone alcohol, n-nonyl acetate, ethylene glycol monoethyl ether acetate, 1, 2-diacetoxyethane, 1-acetoxy-2-methoxyethane, 1, 2-diacetoxypropane, diethylene glycol monomethyl ether acetate, Diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, and the like.
The amount of water and the solvent containing a high boiling point solvent is preferably 100 to 100,000 parts by mass, more preferably 200 to 50,000 parts by mass, based on 100 parts by mass of the thermosetting silicon-containing material (Sx).
[ other ingredients ]
(organic acid)
In order to improve the stability of the composition for forming a silicon-containing resist underlayer film of the present invention, it is preferable to add a mono-or di-or higher organic acid having 1 to 30 carbon atoms. Examples of the acid to be added include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, stearic acid, linoleic acid, linolenic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, dimethylmalonic acid, diethylmalonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, itaconic acid, maleic acid, fumaric acid, conic acid, and citric acid. In particular, oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, citric acid and the like are preferable. In order to ensure stability, 2 or more kinds of acids may be used in combination. The amount of the thermosetting silicon-containing material (Sx) to be added is preferably 0.001 to 25 parts by mass, more preferably 0.01 to 15 parts by mass, and still more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the thermosetting silicon-containing material (Sx) contained in the composition.
Or the organic acid may be blended in such an amount that the pH of the composition becomes 0. ltoreq. pH.ltoreq.7, more preferably 0.3. ltoreq. pH.ltoreq.6.5, still more preferably 0.5. ltoreq. pH.ltoreq.6, in terms of the amount.
(photoacid generators)
The silicon-containing resist underlayer film forming composition of the present invention may further contain a photoacid generator. Specific examples of the photoacid generator used in the present invention include those described in paragraphs (0160) to (0179) of Japanese patent application laid-open No. 2009-126940.
(stabilizers)
A stabilizer may be added to the silicon-containing resist underlayer film forming composition of the present invention. The stabilizer may be added with a monohydric or dihydric or higher alcohol having a cyclic ether as a substituent. In particular, the stability of the silicon-containing resist underlayer film forming composition can be improved by adding the stabilizer described in the paragraphs of jp 2009-126940 a (0181) to (0182).
(surfactant)
The silicon-containing resist underlayer film forming composition of the present invention may contain a surfactant, if necessary. Specifically, the material described in the paragraph of Japanese patent application laid-open No. 2009-126940 (0185) can be added.
[ Pattern Forming method ]
The present invention can provide a pattern forming method (so-called "multilayer resist method") including the steps of: forming an organic underlayer film on a workpiece by using a coating type organic underlayer film material; forming a resist underlayer film on the organic underlayer film by using the silicon-containing resist underlayer film forming composition; forming a resist upper layer film on the silicon-containing resist lower layer film by using a resist upper layer film composition composed of a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring a pattern to the resist underlayer film by etching using the resist underlayer film on which the circuit pattern has been formed as a mask; transferring the pattern to the organic film by etching using the resist underlayer film to which the pattern has been transferred as a mask; and transferring a pattern to the object by etching using the organic film having the transferred pattern as a mask.
Further, the present invention may provide a pattern forming method (so-called "multilayer resist method") including the steps of: forming a hard mask mainly containing carbon on a workpiece by a CVD method; forming a resist underlayer film on the hard mask by using the silicon-containing resist underlayer film forming composition; forming a resist upper layer film on the resist lower layer film by using a resist upper layer film composition composed of a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring a pattern to the resist underlayer film by etching using the resist underlayer film on which the circuit pattern has been formed as a mask; transferring the pattern to the hard mask by dry etching using the resist underlayer film to which the pattern has been transferred as a mask; and transferring the pattern to the workpiece by dry etching using the hard mask to which the pattern has been transferred as a mask.
When a pattern is formed using the silicon-containing resist underlayer film of the present invention, a pattern formed of a photoresist can be formed on a substrate without causing a dimensional change difference by optimizing the combination of the organic underlayer film and the CVD film as described above.
In the positive pattern forming method, a resist upper layer film is formed, exposed to heat, and alkali-developed with an alkali developing solution to obtain a positive resist pattern. Further, it is preferable to perform post-exposure baking (PEB) after exposure. As the alkali developer, tetramethylammonium hydroxide (TMAH) or the like can be used.
The patterning of the resist upper layer film is preferably performed by photolithography with a wavelength of 10nm to 300nm, direct drawing with an electron beam, nano-imprinting, or a combination thereof.
The object to be processed is preferably a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film or a metal oxide nitride film.
The metal constituting the workpiece is preferably silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or an alloy thereof.
The photoresist composition, for example, a resin represented by the following formula and
[ solution 24]
Figure BDA0002465657770000491
A Propylene Glycol Methyl Ether Acetate (PGMEA) solution of an acid generator represented by the following formula.
[ solution 25]
Figure BDA0002465657770000492
After the solution was applied to the resist underlayer film, PGMEA was heated and removed to obtain a substrate having a resist overlayer film with a film thickness of 40nm, KrF excimer laser irradiation was performed to decompose an acid generator to generate acid, the substrate was treated at 150 ℃, the resin was dissolved in an aqueous alkali solution by the action of the acid in the resist overlayer film, and alkali development was performed using an alkali developing solution to obtain a positive resist pattern. In this case, since the diffusion distance of the curing catalyst (Xc) contained in the silicon-containing resist underlayer film forming composition of the present invention to the resist underlayer film is 5nm or less, the generated acid is neutralized by the curing catalyst (Xc), and the film thickness of the resin film remaining on the resist underlayer film is 5nm or less.
[ examples ]
The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these descriptions. In the following examples,% represents mass%, and the molecular weight measurement was performed by GPC.
[ Synthesis example 1]
A mixture of 30.6g of compound (101), 38.1g of compound (102) and 5.9g of compound (110) was added to a mixture of 120g of methanol, 0.1g of 10% nitric acid and 60g of deionized water, and the mixture was kept at 40 ℃ for 12 hours to conduct hydrolytic condensation. After completion of the reaction, 600g of propylene glycol monoethyl ether (PGEE) was added thereto, and water and by-product alcohol to be subjected to hydrolytic condensation were distilled off under reduced pressure to obtain 440g of a PGEE solution of silicone compound 1 (compound concentration: 10%). The molecular weight of the polycarbonate resin was measured in terms of polystyrene, and the Mw was 2,900.
Synthesis examples 2 to 22 were carried out under the same conditions as in Synthesis example 1 using the monomers shown in Table 1 to obtain the respective objects.
[ Table 1]
Synthesis example Reaction raw material Mw
1 Compound (101): 30.6g, Compound (102): 38.1g, Compound (110): 5.9g 2900
2 Compound (101): 30.6g, Compound (102): 38.1g, Compound (111): 6.4g 2300
3 Compound (101): 30.6g, Compound (102): 38.1g, Compound (112): 7.0g 2900
4 Compound (101): 30.6g, Compound (102): 38.1g, Compound (113): 6.6g 2900
5 Compound (101): 30.6g, Compound (102): 38.1g, Compound (114): 7.3g 2100
6 Compound (101): 30.6g, Compound (102): 38.1g, Compound (115): 6.2g 2700
7 Compound (101): 30.6g, Compound (102): 38.1g, Compound (116): 5.1g 2000
8 Compound (101): 30.6g, Compound (102): 38.1g, Compound (117): 6.8g 2300
9 Compound (101): 30.6g, Compound (102): 38.1g, Compound (118): 8.9g 2600
10 Compound (101): 30.6g, Compound (102): 38.1g, Compound (119): 8.0g 2300
11 Compound (100): 5.0g, Compound (101): 30.6g, Compound (102): 38.1g 2500
12 Compound (101): 13.6g, Compound (102): 53.3g, Compound (110): 11.8g 2100
13 Compound (101): 13.6g, Compound (102): 53.3g, Compound (111): 12.7g 2800
14 Compound (101): 13.6g, Compound (102): 53.3g, Compound (112): 13.9g 2500
15 Compound (101): 13.6g, Compound (102): 53.3g, Compound (113): 13.2g 2400
16 Compound (101): 13.6g, Compound (102): 53.3g, Compound (114): 14.5g 2600
17 Compound (101): 13.6g, Compound (102): 53.3g, Compound (115): 12.3g 2300
18 Compound (101): 13.6g, Compound (102): 53.3g, Compound (116): 10.2g 2600
19 Compound (101): 13.6g, Compound (102): 53.3g, Compound (117): 13.5g 2500
20 Compound (101): 13.6g, Compound (102): 53.3g, Compound (118): 17.7g 2700
21 Compound (101): 13.6g to getCompound (102): 53.3g, Compound (119): 16.0g 3000
22 Compound (100): 5.0g, Compound (101): 17.0g, Compound (102): 53.3g 2800
PhSi(OCH3)3Compound (100)
CH3Si(OCH3)3Compound (101)
Si(OCH3)4Compound (102)
[ solution 26]
Figure BDA0002465657770000521
The composition of the silicon-containing films containing the compounds of table 1 is disclosed in table 2 below.
[ Table 2]
Figure BDA0002465657770000531
[ hardening catalyst ]
Figure BDA0002465657770000541
[ solvent ]
PGEE propylene glycol monoethyl ether
PGMEA propylene glycol monomethyl ether acetate
The composition of the solution (C-1) comprising the resin (A) having increased solubility in an alkali developing solution by the action of an acid, an acid generator for generating an acid by a high-energy ray or an electron beam, and a solvent is shown in Table 3.
[ Table 3]
Figure BDA0002465657770000542
The structural formula of the resin (a) shown in table 3 is shown below.
[ solution 27]
Figure BDA0002465657770000551
The structural formula of the acid generator PAG1 shown in table 3 above is shown below.
[ solution 28]
Figure BDA0002465657770000552
[ measurement of diffusion Length (measurement method-1) ]
The silicon-containing resist underlayer Film forming compositions Soln.1 to 31 shown in Table 2 were applied to a substrate and heated at 220 ℃ for 60 seconds to form polysiloxane Film layers Film1 to 31 having a Film thickness of 20 nm.
Then, a solution (C-1) containing the prepared resin (A), an acid generator and a solvent was applied onto the polysiloxane film, and the resultant was baked at 100 ℃ for 60 seconds to form a 40nm thick resin layer resist upper layer film.
Then, they were exposed to an open frame light at an initial dose of 3mJ and a step dose of 0.75mJ using a KrF exposure apparatus (manufactured by Nikon corporation; NSR-206D, NA 0.82.82), subjected to a heat treatment at 150 ℃ for 60 seconds, baked at 70 ℃ for 60 seconds (PEB), and developed with a 2.38 mass% aqueous solution (developer) of tetramethylammonium hydroxide (TMAH) for 30 seconds.
Then, the thickness of the resin remaining on the silicon-containing resist underlayer film without dissolving in the developer was measured by an optical interference type film thickness measuring apparatus (manufactured by SCREEN Co., Ltd.; VM-2200). The obtained film thickness is defined as the diffusion distance of the curing catalyst from the resist underlayer film.
The resin residual film thickness (diffusion distance of the curing catalyst) calculated by the measurement method-1 is shown in Table 4 below.
[ Table 4]
Silicon-containing resist film Resin residual film thickness (nm)
Example 1 Film1 3.6
Example 2 Film2 3.5
Example 3 Film3 3.6
Example 4 Film4 3.6
Example 5 Film5 3.6
Example 6 Film6 3.5
Example 7 Film7 3.5
Example 8 Film8 3.6
Example 9 Film9 3.6
Example 10 Film10 3.5
Example 11 Film11 3.3
Example 12 Film12 3.6
Example 13 Film13 3.5
Example 14 Film14 3.6
Example 15 Film15 3.6
Example 16 Film16 3.4
Example 17 Film17 3.4
Example 18 Film18 3.5
Example 19 Film19 3.6
Example 20 Film20 3.6
Example 21 Film21 3.6
Example 22 Film22 3.6
Example 23 Film23 3.3
Example 24 Film24 2.7
Example 25 Film25 1.4
Example 26 Film26 1.5
Example 27 Film27 1.4
Example 28 Film28 1.5
Comparative example 1 Film29 12.1
Comparative example 2 Film30 11.7
Comparative example 3 Film31 7.5
As is clear from Table 4, the diffusion distance of the curing catalyst contained in the silicon-containing resist underlayer film forming compositions of examples 1 to 28 from the resist underlayer film to the resist overlayer film was 5nm or less. On the other hand, the diffusion distance of the curing catalyst contained in the silicon-containing resist underlayer film forming composition of comparative examples 1 to 3 from the resist underlayer film to the resist overlayer film was 5nm or more.
[ EUV patterning test ]
Silicon wafers were spin-coated with the silicon-containing resist underlayer Film forming compositions Soln.1 to 31 shown in Table 2 on Si substrates and heated at 220 ℃ for 60 seconds to obtain silicon-containing films Film1 to 31 having a Film thickness of 20 nm.
Then, a resist material obtained by dissolving the following resin, quencher and sensitizer in an organic solvent composed of PGMEA, cyclohexanone (CyHO) and PGME at the ratio shown in table 5 was spin-coated on the silicon-containing resist underlayer film, and was prebaked at 105 ℃ for 60 seconds using a hot plate to obtain a resist upper layer film having a film thickness of 60 nm. The substrate was exposed to light using an EUV scanner NXE3300(NA0.33, σ 0.9/0.6, quadrupole illumination, mask of hole pattern with a size of 46nm, + 20% on wafer) manufactured by ASML corporation, and subjected to PEB at 100 ℃ for 60 seconds on a hot plate and development with 2.38 mass% TMAH aqueous solution for 30 seconds to obtain a hole pattern with a size of 23 nm.
When the pores were formed at 23nm, the size of 50 pores was measured by using a length measuring SEM (CG5000) manufactured by Hitachi technologies, and the size variation (CDU, 3. sigma.) was determined. The results are shown in Table 6.
[ solution 29]
Figure BDA0002465657770000591
Surfactant (b): FC-4430 manufactured by 3M
[ Table 5]
Figure BDA0002465657770000592
[ Table 6]
Silicon-containing resist film CDU(nm)
Example 29 Film1 2.4
Example 30 Film2 2.4
Example 31 Film3 2.3
Example 32 Film4 2.3
Example 33 Film5 2.4
Example 34 Film6 2.3
Example 35 Film7 2.3
Example 36 Film8 2.4
Example 37 Film9 2.4
Example 38 Film10 2.3
Example 39 Film11 2.3
Example 40 Film12 2.3
EXAMPLE 41 Film13 2.3
Example 42 Film14 2.4
Example 43 Film15 2.3
Example 44 Film16 2.3
Example 45 Film17 2.3
Example 46 Film18 2.3
Example 47 Film19 2.3
Example 48 Film20 2.4
Example 49 Film21 2.3
Example 50 Film22 2.3
Example 51 Film23 2.3
Example 52 Film24 2.3
Example 53 Film25 2.3
Example 54 Film26 2.4
Example 55 Film27 2.3
Example 56 Film28 2.3
Comparative example 4 Film29 3.1
Comparative example 5 Film30 3.0
Comparative example 6 Film31 3.1
As in comparative examples 4 to 6 of table 6, the curing catalyst having a diffusion distance longer than 5nm (the number of carbon atoms of the organic group constituting the cationic portion of the curing catalyst contained in the resist underlayer film is 8 or less) causes uneven diffusion in the upper layer resist due to the long diffusion distance, resulting in deterioration of CDU. On the other hand, it is understood that the compositions for forming a silicon-containing underlayer resist film of examples 29 to 56, which used the curing catalyst having a diffusion distance of 5nm or less, exhibited excellent CDU.
[ ArF patterning test ]
A spin-on carbon film ODL-102 (carbon content: 89 mass%) was formed on a silicon wafer to a film thickness of 200 nm. A silicon-containing resist underlayer Film forming composition Soln.1 to 31 is applied on the spin-on carbon Film, and heated at 220 ℃ for 60 seconds to form a polysiloxane Film1 to 31 having a Film thickness of 20 nm.
Then, an ArF resist solution (PR-1) for positive development having the composition shown in Table 7 and containing the following ArF resist polymer 1, acid generator, quencher and surfactant was applied onto the resist underlayer film, and the resultant film was baked at 110 ℃ for 60 seconds to form a resist underlayer film having a thickness of 100 nm.
[ solution 30]
Figure BDA0002465657770000611
Surfactant (b): FC-4430 manufactured by 3M
[ Table 7]
Figure BDA0002465657770000621
Then, a resist upper layer film was coated with a wet protective film (TC-1) having a composition shown in Table 8 and containing the following protective polymers, and the resultant was baked at 90 ℃ for 60 seconds to form a protective film having a film thickness of 50 nm.
[ solution 31]
Figure BDA0002465657770000622
[ Table 8]
Figure BDA0002465657770000623
Then, they were exposed to light using an ArF immersion exposure apparatus (manufactured by ASML Co., Ltd.; XT-1900i, NA1.35,. sigma.0.97/0.77, 35 degree dipolar polarized illumination), baked at 100 ℃ for 60 seconds (PEB), and developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds to obtain a resist pattern of 40nm 1: 1 positive pattern of lines and spaces. The dimensions of LWR were observed with a Hitachi-Tech (stock) electron microscope (CG5000), and the cross-sectional shape was observed with a Hitachi-Tech (stock) electron microscope (S-9380). The results are shown in Table 9.
[ Table 9]
Silicon-containing resist film Cross-sectional shape of pattern after development LWR(nm)
Example 57 Film1 Vertical shape 2.4
Example 58 Film2 Vertical shape 2.4
Example 59 Film3 Vertical shape 2.3
Example 60 Film4 Vertical shape 2.3
Example 61 Film5 Vertical shape 2.4
Example 62 Film6 Vertical shape 2.3
Example 63 Film7 Vertical shape 2.3
Example 64 Film8 Vertical shape 2.4
Example 65 Film9 Vertical shape 2.4
Example 66 Film10 Vertical shape 2.3
Example 67 Film11 Vertical shape 2.3
Example 68 Film12 Vertical shape 2.3
Example 69 Film13 Vertical shape 2.3
Example 70 Film14 Vertical shape 2.4
Example 71 Film15 Vertical shape 2.3
Example 72 Film16 Vertical shape 2.3
Example 73 Film17 Vertical shape 2.3
Example 74 Film18 Vertical shape 2.3
Example 75 Film19 Vertical shape 2.3
Example 76 Film20 Vertical shape 2.4
Example 77 Film21 Vertical shape 2.3
Example 78 Film22 Vertical shape 2.3
Example 79 Film23 Vertical shape 2.3
Example 80 Film24 Vertical shape 2.3
Example 81 Film25 Vertical shape 2.2
Example 82 Film26 Vertical shape 2.2
Example 83 Film27 Vertical shape 2.2
Example 84 Film28 Vertical shape 2.2
Comparative example 7 Film29 Trailing shape 2.7
Comparative example 8 Film30 Trailing shape 2.8
Comparative example 9 Film31 Trailing shape 2.8
As shown in comparative examples 7 to 9 of Table 9, the curing catalyst having a diffusion distance longer than 5nm is unevenly diffused toward the upper layer resist due to its long diffusion distance, and causes the deterioration of LWR. On the other hand, the silicon-containing underlayer resist film forming compositions of examples 57 to 84, which used the curing catalyst having a diffusion distance of 5nm or less, exhibited good LWRs.
As described above, the short diffusion distance hardening catalyst (Xc) contained in the silicon-containing resist underlayer film of the present invention can suppress diffusion into the resist underlayer film, and thus, the hardening catalyst (Xc) that does not affect LWR and CDU in EUV lithography and the silicon-containing resist underlayer film forming composition containing the hardening catalyst (Xc) can be selected.
The present invention is not limited to the above-described embodiments. The above embodiments are illustrative, and any configuration that has substantially the same technical idea as the technical idea described in the claims of the present invention and exerts the same effects is included in the technical scope of the present invention.
[ notation ] to show
1: substrate
Silicon-containing resist underlayer film
3 resist top layer film
4 residual resist top layer film

Claims (8)

1. A silicon-containing resist underlayer film forming composition comprising a thermosetting silicon-containing material (Sx), a curing catalyst (Xc) and a solvent,
the hardening catalyst (Xc) has a diffusion distance of 5nm or less from a resist underlayer film formed from the silicon-containing resist underlayer film forming composition to a resist overlayer film formed on the resist underlayer film.
2. The silicon-containing resist underlayer film forming composition according to claim 1, wherein the curing catalyst (Xc) is a sulfonium salt (Xc-1), an iodonium salt (Xc-2), a phosphonium salt (Xc-3), an ammonium salt (Xc-4), or a polysiloxane (Xc-10) having these as a partial structure, or an alkali metal salt.
3. The composition for forming a silicon-containing resist underlayer film according to claim 2, wherein the total number of carbon atoms contained in the organic group forming the cationic moiety of the curing catalyst (Xc) is 9 or more.
4. A pattern forming method comprising the steps of:
forming an organic film on a workpiece by using a coating type organic film material;
forming a resist underlayer film using the silicon-containing resist underlayer film forming composition according to any one of claims 1 to 3 over the organic film;
forming a resist upper layer film on the resist lower layer film by using a resist upper layer film composition composed of a photoresist composition;
forming a circuit pattern on the resist upper layer film;
transferring a pattern to the resist underlayer film by etching using the resist overlayer film on which the circuit pattern has been formed as a mask;
transferring the pattern to an organic film by etching using the resist underlayer film to which the pattern has been transferred as a mask;
and transferring the pattern to the object to be processed by etching using the organic film to which the pattern has been transferred as a mask.
5. A pattern forming method comprising the steps of:
Forming a hard mask mainly containing carbon on a workpiece by a CVD method;
forming a resist underlayer film using the silicon-containing resist underlayer film forming composition according to any one of claims 1 to 3 over the hard mask;
forming a resist upper layer film on the resist lower layer film using a resist upper layer film composition composed of a photoresist composition;
forming a circuit pattern on the resist upper layer film;
transferring a pattern to the resist underlayer film by etching using the resist overlayer film on which the circuit pattern has been formed as a mask;
transferring the pattern to the hard mask by dry etching using the resist underlayer film to which the pattern has been transferred as a mask;
transferring the pattern to the object to be processed by dry etching using the hard mask to which the pattern has been transferred as a mask.
6. The pattern forming method according to claim 4 or 5, wherein the patterning of the resist upper layer film is performed by photolithography with a wavelength of 10nm to 300nm, direct writing with an electron beam, nano-imprinting, or a combination thereof.
7. The pattern forming method according to claim 4 or 5, wherein the object to be processed is a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, or a metal oxynitride film.
8. The pattern forming method according to claim 4 or 5, wherein the metal constituting the body to be processed is silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or an alloy thereof.
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